"Paulo Bento and the rest of the technical staff have signed a contract valid until July 2012," the Portuguese Football Federation (FPF) said in a statement.
The FPF will hold a news conference on Wednesday to officially unveil the new coaching team.
Queiroz was sacked in the wake of his six-month suspension for insulting anti-doping agents before the World Cup.
Bento's first games in charge will be the Euro qualifiers on October 8 at home to Denmark and in Iceland four days later.
Portugal will be under pressure to win both matches and give themselves a realistic chance of qualifying after getting off to a dismal start with a 4-4 home draw with Cyprus followed by a 1-0 defeat in Norway earlier this month.
"I'm very satisfied with the appointment. It is another problem solved. We have to believe we can qualify for the European Championship," FPF chief Gilberto Madail told reporters.
Madail last week flew to Madrid to try to persuade Jose Mourinho to take the job temporarily for the October qualifiers but the coach's club Real Madrid were against the idea.
Bento's only coaching experience was a four-year stint at Sporting from 2005 although he was widely considered a success with four consecutive runners-up spots in the Portuguese League and a haul of two Portuguese Cups.
During that spell, Bento became known as a tough-talking disciplinarian, never shying away from clamping down on bad behaviour by his players including top striker Liedson.
He also won plaudits for promoting players from Sporting's youth academy. Some of them, like winger Nani and midfielders Joao Moutinho and Miguel Veloso, are now likely to feature in Bento's Portugal squad.
In November 2009, he resigned as Sporting coach following a weak start to the season and has not coached since.
Bento started his playing career as a defensive midfielder at Estrela da Amadora in 1989 and then played for Guimaraes, Benfica and Spain's Oviedo, before retiring in 2004 after four seasons at Sporting.
At Euro 2000 Bento, who won 35 caps, got a six-month ban for aggressive conduct towards the referee after Portugal's semi-final exit and retired from the national side after playing in the 2002 World Cup.
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