Ian Poulter and Nicolas Colsaerts have received the two wildcard picks as captain Jose Maria Olazabal completed his 2012 European Ryder Cup side.
England's Poulter, 36, will be winning his fourth cap, while Belgian Colsaerts, 29, will make his debut in Medinah, Chicago from 28-30 September.
The pair joined the 10 automatic picks from the rankings after Sunday's Johnnie Walker Championship.
Europe have beaten the United States in four of the last five Ryder Cups.
The players who made the team by right are Rory McIlroy, Justin Rose, Graeme McDowell, Paul Lawrie, Francesco Molinari, Luke Donald, Lee Westwood, Sergio Garcia, Peter Hanson and Martin Kaymer.
The US-based Poulter, who struggled with pneumonia earlier this season, has built a reputation as a fearsome matchplay exponent. He was the highest points scorer for either side when selected as a wildcard for the 2008 Ryder Cup at Valhalla and won three points out of four in Europe's 14½-13½ win at Celtic Manor two years ago.
Poulter, who made the first of his three previous appearances in the biennial event in 2004, could have overhauled the Germany's former world number one Kaymer with a 35th-place finish in Scotland, but opted to stay in America.
Colsaerts, who won the World Match Play Championship in May, could also have sealed an automatic place with a top-two finish at Gleneagles, but his share of 19th meant the out-of-form Kaymer held on to the final qualification place, despite also opting to miss the event.
The 29-year-old Colsaerts, the longest hitter on the European Tour, is the next man on the Ryder Cup rankings list and is considered the leading contender for the final spot.
Colsaerts will become the first Belgian to compete in the Ryder Cup and will also be the only rookie in this year's side, compared to the six that played in Wales.
Padraig Harrington, a six-time Ryder Cup veteran, was also in contention for a wildcard - but Olazabal said it would take "at least a win" at the Barclays tournament in New York for the Irishman to stand a chance, but he finished eight shots behind eventual winner Nick Watney.
The 10 automatic choices were made up of the top five from a list based on ranking points won in European Tour events, followed by the next five best on the world rankings.
Olazabal, who played in seven Ryder Cups from 1987-2006 and was a key partner of the late Seve Ballesteros, will have four vice-captains to assist him in Chicago.
The two-time Masters champion will be joined by Northern Ireland's Darren Clarke, Ireland's Paul McGinley, Denmark's Thomas Bjorn and Spain's Miguel Angel Jimenez.
Eight players have already qualified for the US team: Tiger Woods, Bubba Watson, Jason Dufner, Keegan Bradley, Webb Simpson, Zach Johnson, Matt Kuchar and Phil Mickelson.
US captain Davis Love names his four wildcard choices on 3 September after the first two events of the PGA Tour's FedEx Cup play-offs.
The 2012 Ryder Cup will take place from 28-30 September at Medinah Country Club in Illinois.
