The 47-year-old revealed her decision after picking up three points from four matches as an 11th-hour replacement in the 16.5-11.5 defeat in Des Moines.
“This is going to be my last one playing,” declared the Scottish No 1 at the end of her ninth appearance against the Americans.
Referring to her last-day singles win over Stacy Lewis, she added: “You know, I was 3-down through 11 and I kind of said to myself, ‘this is going to be my last match’.
“So I gave it my all and managed to squeak a win. I enjoyed the moment today, but I think it’s time for some younger players to take over.”
Matthew is bowing as Europe’s third most-successful player in the event, having taken her tally to 22 points here in Iowa.
She’s just three behind the all-time points scorer, Laura Davies, and two behind Annika Sorenstam, her captain in this event.
Matthew made her debut in the match in 1998 and has appeared on three winning teams - in 2003, 2011 and 2013. She secured Europe’s first win on US soil in the latter in Denver.
The Scot’s last-day success here wasn’t enough to allow Europe to overcome a five-point deficit heading into the singles.
The defeat means the Americans will now be heading to Scotland, where the match is being held for a third time, in 2019 bidding for a third title hat-trick in the event.
Matthew echoed her captain, though, when she said the visitors had been far from down-hearted by this week’s result against a strong US side.
“We felt like last time in Germany that we had lost it,” she said of seeing the Americans recover from being 10-6 down to prevail. “This time we don’t feel as we lost it. They just played better than us.
“We played well, but they just played some amazing golf. We had a fantastic team, a great captain in Annika. So I think we’ve just got to take the positives from it.”
Matthew won’t have the Swede as a rival for the Gleneagles captaincy as the former world No 1 immediately ruled herself out of the reckoning for that.
“It’s a one-time show,” she said. “It’s been a great journey and so forth. But we have so many wonderful candidates lining up, and it’s an honor to do this. And I would love somebody else to get the opportunity to do this.
“The European team will always have a place in my heart. And this week will, too. But it is time to move on.”