Damien Hoyland scored a hat-trick on his return to international rugby and there was a double for George Horne before late tries from Rufus McLean and replacement Ali Price added some gloss.
Stiffer tests await Gregor Townsend's side in the form of a three-Test series in Argentina but the Scotland coach will be satisfied with the way this tour opener unfolded.
Three uncapped players started and another three came off the bench. How many of Ben Muncaster, Ollie Smith, Matt Currie, Johnny Matthews, Murphy Walker and Glen Young impressed enough to remain in the squad to face the Pumas remains to be seen. Townsend's intention is to trim his touring party this week and the new boys face an anxious few days.
With the exception of Scarlets prop Javan Sebastian, this was a Scotland team comprising players from Edinburgh and Glasgow Warriors and the absence of the English-based exiles contributed to its status as a non-cap international.
For Chile, it was a more notable occasion - their first meeting with a Six Nations side since 1954 and a chance to play Tier 1 opposition ahead of their two-legged World Cup play-off against the United States.
The opening skirmishes were cagey. Townsend had said they would try to move Chile around the field and Scotland kicked a lot of early ball.
It took then nearly ten minutes to find their way into the Chilean 22 but when they got there they made it count. And it was a moment to savour for Hoyland. Five years after his last appearance for Scotland, the Edinburgh winger marked his return to international rugby with a try. It was a straightforward execution, Sione Tuipulotu slinging the ball back to Ross Thompson who fed Smith who played in Hoyland to score in the corner.
Thompson converted from wide on the right to put Scotland 7-0 ahead.
The try seemed to have a settling effect on the visitors who quickly plundered two more, both from Horne.
The scrum-half tends to score his tries in bunches - he got a double on the last visit to Argentina back in 2018 and a hat-trick against Russia at the 2019 World Cup - and he almost had a first-half treble in Santiago.
As it was, he had to be content with two in six minutes. The first was down to the work of captain Luke Crosbie who burst through some half-hearted tackle attempts before passing to Horne who ran in under the posts.
His second try came courtesy of a lovely dummy. Matt Fagerson had set the ball after a tackle and Horne fooled three Chileans as he pretended to pass before darting over.
Scotland, who were 21 points to the good at the halfway point of the half, were starting to find pockets of space all over the pitch and thought they had scored a fourth try in the 26th minute.
McLean was architect and finisher, kicking ahead and then gathering the ball after the bounce just eluded Horne who must have thought the hat-trick was his. Unfortunately for McLean and Scotland, the scrum-half had made a slight connection with his left arm, knocking the ball forward just before the winger caught it.
Credit to Horne, who fessed up to referee Adam Jones who chalked off the score.
Scotland continued to go at Chile and both Muncaster and Jamie Bhatti were held up over the line by some impressively heroic defending. The tourists were patient, and when Dave Cherry and Scott Cummings were both stopped short Scotland kept recycling until Hoyland found the gap to run in his second try just before half-time.
The hat-trick wasn’t long in coming for the Edinburgh man. Only four minutes of the second half had elapsed when Cumming went marauding down the right. The lock, returning from injury, showed impressive deftness to feed the supporting Hoyland with a one-handed pass and the winger had enough strength to reach out and touch the ball down despite the valiant attempt by Alfonso Escobar to stop him.
Thompson was off target with the conversion attempt from the right-hand touchline, his first miss of the night.
Chile had offered little in an attacking sense in the first 60 minutes but they squandered a glorious chance just after the hour mark. They had Scotland on the back foot and looked to have a numerical advantage on the right flank only for stand-off Rodrigo Fernandez to throw the ball wildly out of play.
The crowd in the Estadio Santa Laura Universidad SEK had been roused and Chile seemed suddenly galvanised. Scotland were having to defend with all their might and Townsend summoned the cavalry from the bench. The experienced trio of Pierre Schoeman, Price and Blair Kinghorn joined the fray with 12 minutes remaining as the visitors tried to regain momentum.
It never quite happened and Chile got the try their play in the final quarter deserved when Santiago Edwards plunged over from close range after replacement Santiago Videla had been stopped by Price a yard from the line.
The score prompted wild celebrations but Scotland had the final say, notching two late tries.
McLean got the first, sprinting into the corner after Kinghorn had found him with a long, looped pass.
Bennett and Price then combined to set up the scrum-half for the game’s final score which Kinghorn converted.
Scorers: Chile: Try: Edwards. Scotland: Tries: Hoyland 3, Horne 2, McLean, Price. Cons: Thompson 4, Kinghorn.
Chile: F Urroz; N Garafulic (N Herreros 56), P Casas, I Ayarza, M Garafulic; R Fernandez, M Torrealba (J Larenas 47); J Carrasco (S Lues 40), T Dussaillant (D Escobar 25), V Lastra (I Gurruchaga 59), S Pedro, C Saavedra (T Orchard 13), S Edwards, I Silva (R Martinez 40), A Escobar (S Videla 47).
Scotland A: O Smith; D Hoyland, M Currie (M Bennett 68), S Tuipulotu, R McLean; R Thompson (B Kinghorn 68), G Horne (A Price 68); J Bhatti (P Schoeman 68), D Cherry (J Matthews 52), J Sebastian (M Walker 58), J Hodgson, S Cummings (G Young 52), B Muncaster, L Crosbie (c), M Fagerson (M Bradbury 52).
Referee: Adam Jones (Wales).