Craig Levein paid for a poor run of results when he was sacked as Scotland manager by the Scottish Football Association (SFA) on Monday.
"The Scottish FA tonight announces that Craig Levein has been relieved of his duties as Scotland National Coach," said an SFA statement.
"The board of the Scottish FA has taken the decision primarily due to the disappointing results in the FIFA World Cup Brazil 2014™ Qualifiers, which have culminated in Scotland being bottom of the group after four matches."
Former Scotland defender Levein guided the Scots to just three wins in his 12 competitive matches in charge after replacing fellow former international George Burley in 2009. Their chances of reaching the finals of a major tournament for the first time since the 1998 FIFA World Cup in France are hanging by a thread.
Scotland U-21 coach Billy Stark will take caretaker charge of the senior side for next week's friendly away to Luxembourg.
Following a meeting of the SFA board at Glasgow's Hampden Park, chief executive Stewart Regan said in a statement: "We are taking this decision with real sadness. Craig has worked hard to bring success, and has been thoroughly professional in his approach to the job.
"He has achieved a great deal with the team and in other areas, such as the performance strategy. However, he would be the first to agree that football is a results-driven business. For that reason we have relieved Craig of his duties with immediate effect.
"After the Luxembourg match, the board will meet to begin the process of identifying and recruiting the next national coach to take us forward. We will give ourselves time, given our fixture schedule, to find the right person for the job.
Recent defeats by both Wales and Belgium had piled the pressure on Levein. But he'd lost the support of many fans early in his time as Scotland manager by opting for a 4-6-0 formation - playing without a recognised striker - in a 1-0 defeat away to the Czech Republic, Scotland's main rivals for a UEFA EURO 2012 play-off place.
However, the scale of the problem confronting Scotland is that a full-time successor to former Hearts and Dundee United boss Levein will be their eighth manager already this century.
Former Scotland midfielder Gordon Strachan, currently out-of-work, has long been tipped as the favourite to replace Levein. Strachan, who played under Alex Ferguson at both Aberdeen and Manchester United, has previously been in charge of Glasgow giants Celtic and has also managed in the English Premier League at Coventry and Southampton.