After starting out on an overcast morning in drizzle, Matthew and Caithness signed for a three-under-par 69 in a fourball betterball format and were lying in a tie for ninth alongside Welsh duo Becky Brewerton and Breanne Loucks at the end of the first day.
Matthew, who had only arrived at the La Sella Resort in Dnia, Alicante, on Wednesday afternoon, rolled in a 25-foot birdie putt at the second before the British Women's champion also birdied the third. Caithness, playing in the team event for the first time, also played her part with birdies at the ninth and 11th holes, with the only blemish on the Scots' card coming at the par-4 13th, where both players took bogeys.
Despite that, they went into today's second round just three shots off the lead, which is being held by Austrian duo Nicole Gergely and Stefanie Michl and Spain's Tania Elosegui and Emma Cabrera Bello.
"It was not too bad, but a little bit scrappy on the back nine," said Matthew. "We didn't combine as well as we could have."
Today's second round will be played as 'Valencian Cup', which is a variation on greensomes where players tee off then switch and play their partner's ball for the next shot (on par 4s) and for the next 2 shots (on par 5s) before selecting the best ball and completing the hole in alternate shot (foursome) format. On par 3s the best tee shot is selected before completing the hole with alternate shots. "It is the kind of format you can go out and shoot a low one," said Matthew.