The 50-year-old is a veteran of nine Solheim Cups as a player and said the event has been "the highlight of my career every two years".
There are three rookies in the European team, in Anne Van Dam, Celine Boutier and Bronte Law, but seven players who have featured in at least three Solheim Cups.
The Korda sisters, meanwhile, will become the first pair of siblings to compete for Team USA at the Solheim Cup.
"There are no forced fist pumps, no forced emotions", said the former Women's British Open champion and two-time Solheim Cup player Karen Stupples.
"Six rookies, but six great rookies", was how 59-year-old Inkster summed up the situation.
The Stockport-born player picked up her first LPGA Tour victory earlier this season and was one of Matthew's four wildcard picks, along with Boutier, Ewart Shadoff and Suzann Pettersen.
Kang, 26, said she expects to be booed when play gets under way tomorrow and although she later claimed to be joking about the prospect of a hostile reception, there is no doubt she will not back down from a fight. They were only narrowly beaten in Germany four years ago when the U.S. had a much stronger and more-experienced squad and four of their five previous victories have come on European soil.
The visitors are led by Juli Inkster, who is captaining a relatively inexperienced side for a record third time. "And I'm pretty sure I wouldn't have gotten that insight if she wasn't assistant captain". All three were playing on American soil.
Even the alternate who replaced Stacy Lewis - Ally McDonald - is a rookie. There is not quite so much expectation, so the team can play a little looser. It's the bonding you create.
Nelly, the current world No. 10, has racked up three wins since turning professional in 2016. Away from the more hum-drum environments of the week-to-week strokeplay occasions, which can often be greeted with the kind of genteel, polite applause you'd get when Phyllis finishes a slide show of her prize blooms at the local floral art club, the Solheim Cup can be a histrionic hoo-ha during which the traditionally reserved Royal & Ancient game bursts from its straitjacket and goes berserk. "No, we want it lovely weather so the galleries can get out there and enjoy themselves and just cheer us on and be the 13th man out there, because that's what the home-soil advantage gives you".
'Now we're in Scotland, I don't know what I'm going to hear.
The American team also features world number three Lexi Thompson.
Morgan Pressel is the most experienced of the USA players and is making her sixth appearance.
The first Solheim Cup was staged at Lake Nona, Florida in 1990.
Throw in the fact that the Americans have lost both of their previous matches in Scotland - at Dalmahoy in 1992 and at Loch Lomond in 2000 - and there's a lot going the European team's way.
Matthew secured the winning half-point for Europe in that 18-10 triumph, but can the Scot - Europe's third all-time leading points scorer - skipper the hosts back to winning ways? "In (strokeplay) golf, we lose most of the time".
The PGA Centenary course hosted the 2014 Ryder Cup, when Europe's men beat their U.S. counterparts 16½-11½ and there are a number of holes that could be key to the outcome of matches. A heavily contoured green means there's no certainty you'll get down in two.
Named after golf club innovator Karsten Solheim, the Solheim Cup is a biennial match between professional women golfers of the U.S. and Europe.