Casey (left) and Poulter earn their third and second caps respectively
European Ryder Cup captain Nick Faldo handed his two wildcards to England's Paul Casey and Ian Poulter.
The pair complete the 12-strong team after Justin Rose, Soren Hansen and Oliver Wilson sealed the last three automatic spots at Gleneagles.
The decision means Colin Montgomerie misses out on making a ninth Ryder Cup team, while five-time Cup veteran Darren Clarke was also left out.
"I feel very good about those two picks," said Faldo.
"It's been on my mind a long time and these last couple of weeks, and this has been the big day, the day you want to get over.
I'm absolutely overwhelmed. It's awesome. I'll bring excitement, I'll bring flair and I'll bring the passion
"I know how to talk to golfers, and as a golfer I've been there, done that, but to have to make a decision that obviously guys will be emotional about either way is tough.
"I am now very excited, I have got a team and I can now talk to my team. I will start giving them a few thoughts and ask them a few questions on what they want to do and start getting some communciation lines open."
Padraig Harrington, Sergio Garcia, Lee Westwood, Henrik Stenson, Robert Karlsson, Miguel Angel Jimenez and Graeme McDowell have already made the team.
2008 European Ryder Cup team
Padraig Harrington (Ire)
Lee Westwood (Eng)
Sergio Garcia (Spa)
Henrik Stenson (Swe)
Robert Karlsson (Swe)
Miguel Angel Jimenez (Spa)
Graeme McDowell (NIre)
Justin Rose (Eng)
Soren Hansen (Den)
Oliver Wilson (Eng)
Ian Poulter (Eng)
Paul Casey (Eng)
Captain: Nick Faldo (Eng)
Casey, 31, has played in the last two Ryder Cups, while Poulter, 32, who last competed in the 2004 match at Oakland Hills, caught Faldo's eye with a runner-up place at the Open at Royal Birkdale.
"I've been watching these guys through the summer," said Faldo.
"Ian is a very determined guy, I love his attitude and what he did at the Open - that back nine he played with the intention to win and had that emotional feeling."
On Casey, Faldo said: "I was waiting for the putting to turn around. That has been very important.
"He's a former World Matchplay champion, he has an extremely good record in the Ryder Cup and, going back, the Walker Cup."
Poulter chose not to fly back from America for the last qualifying event, this weekend's Johnnie Walker Championship at Gleneagles.
He could have qualified for the team by right with a third-place finish, and his decision not to attend drew widespread criticism.
"It was such a tough decision to make and it might have been the wrong decision looking back. Maybe I should have gone to play Gleneagles," said Poulter.
"I'm absolutely overwhelmed. It's awesome. I'll bring excitement, I'll bring flair and I'll bring the passion I always play golf with and I think that will be an asset to the team."
The guys he picked are really good. His dilemma is a nice one to have
US captain Paul Azinger
Casey was similarly delighted by his wildcard, and said: "It is very flattering considering the large number of in-form players Nick had to choose from.
"I have had the fantastic experience of being part of two winning European Ryder Cup sides and hope that we can make it a third at Valhalla."
Clarke, who played heroically as a wildcard at the K Club two years ago shortly after the death of his wife Heather, was favourite for a pick after winning in Holland last week.
"Nick rang me after my last round at Gleneagles to say that I wasn't going to be one of his picks and I simply wished him all the best," Clarke said.
"Obviously I am disappointed that I wasn't selected but I have dealt with much worse and it will make me all the more determined to make the team that will play in Wales next time (2010).
"I would like to wish him and his team all the very best for Valhalla. I will be supporting them from wherever I am."
Montgomerie, who is expected to captain the European team at Gleneagles in 2014, has been a talisman of the side for a decade and has never lost a singles match.
His omission means there are no Scots in the team for the first time since 1937. If Montgomerie has played in his last Ryder Cup, he will end up two points short of Faldo's record total of 25.
"Monty's summer wasn't great and when I am looking at 10 guys (automatic qualifiers) I'm looking to what to add to the team," said Faldo.
Montgomerie added: "Although I am, of course, very disappointed not to have played my way into the team or into contention for a pick, I am delighted at the obvious strength and depth of the European team," he said.
"I wish Nick and the team the very best of luck and while I shall certainly feel sad not to be playing a part, as I sit glued to the TV I know the overwhelming emotion I will be feeling is pride."
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