The England and Wales Cricket Board said Collingwood, 34, would remain as England's Twenty20 captain and play for England's one-day team.
Collingwood's announcement comes in the midst of a poor Ashes series, scoring just 83 runs from six innings at the number five batting position.
"Representing England at Test level has always been a dream of mine and I've been fortunate enough to have enjoyed some amazing highs throughout my Test career," Collingwood said in a statement.
"I'm proud of the fact that I've always given my all for the England Test team.
"But I feel that this is the right time to leave Test cricket having reached some very special achievements, none more satisfying that retaining the Ashes in Australia.
"I also feel now is the time to ensure some of the younger players are given an opportunity at Test level as we have a wealth of talent pushing for places in the England Test team.
"Clearly I still feel I have a huge amount to offer England in terms of limited overs cricket and I'm looking forward to the opportunity to continue leading the Twenty20 squad and playing a significant role in England's ODI team."
Collingwood made his Test debut in 2003 against Sri Lanka at Galle and has earned 68 caps.
The Durham right-hander has scored 4,259 runs in Tests at 40.95 and taken 17 wickets.
England retained the Ashes after beating Australia in last week's fourth Melbourne Test and are on top in the current final Sydney Test, set to become the first England team to win a series in Australia for 24 years.
Collingwood led England to their first-ever success in a global tournament when his team defeated Australia by seven wickets in the World Twenty20 final in Barbados last May.
Hugh Morris, Managing Director of England Cricket, said: "Paul Collingwood has made an outstanding contribution to the England Test team.
"His performances have been admired and recognised by his teammates and England supporters over many years and his tireless commitment in the Test match arena will be something he will always be remembered for.
"I'm delighted that Paul will be available to continue to make important contributions to our ODI and Twenty20 teams."