The man known as Big Phil kicks off his second stint as Brazil coach against England, a team he saw off in three major tournaments in a row between 2002 and 2006, at Wembley in one of around 40 international friendlies being played this week.
Other heavyweight clashes include world and European champions Spain against South American champions Uruguay in Qatar, France's meeting with Germany at the Stade de France and Netherlands against Italy at the Amsterdam Arena.
Elsewhere, Lionel Messi, who last year equalled Gabriel Batistuta's calendar-year scoring record of 12 goals for Argentina, will take aim at Sweden while Portugal are hoping for a reversal of fortune against in-form Ecuador.
Portugal have failed to win in their last three matches while Ecuador are unbeaten in six games and enjoying a best-ever 12th place in the FIFA rankings, six places above 2014 World Cup hosts Brazil.
"This is the last test before two extremely important matches next month against Israel and Azerbaijan," Portugal coach Paulo Duarte said. "The objective is to improve in-game situations that have been failing."
Ecuador coach Reinaldo Rueda, whose side are second in the South American World Cup qualifying group, added: "Portugal will be a good yardstick."
Spain is a popular venue with Chile facing Egypt at Madrid's Vicente Calderon stadium, Russia and Iceland clashing in Marbella and Romania taking on Australia in Malaga.
Chile will be looking for their third successive win since Jorge Sampaoli, regarded as a disciple of their former coach Marcelo Bielsa, replaced Claudio Borghi.
Belgium's much-heralded new generation host Slovakia but will be without injured defender Vincent Kompany.
Scolari, who led Brazil to their fifth world title in 2002 and was called back in November to lead their attempt to win a sixth on home soil next year, has brought back Ronaldinho and goalkeeper Julio Cesar for his first game back in the hot seat.
The charismatic coach has replaced Mano Menezes who was surprisingly fired in November just as he seemed to be making progress in his efforts to rebuild the side following their 2010 World Cup failure.
Scolari enjoyed a quarter-final win over England as coach of Brazil at the 2002 World Cup and also eliminated them as coach of Portugal at the same stages of Euro 2004 and the 2006 World Cup.
England's last win against Brazil was at Wembley in March 1990, with Brazil winning four of the eight meeting since then.
Scolari is expected to give his side a more rugged style than Menezes, who had been trying to create a Brazilian version of Spain and Barcelona's tiki-taka.
Menezes had even dabbled with the idea of playing without a recognised striker, something Scolari quickly reversed by naming Fred and Luis Fabiano in his squad.
"I always like to have a stronger type of player in the penalty area but it doesn't mean to say we can't change in the future and not have a fixed striker," Scolari said.
Meanwhile, Spain have included Malaga's promising playmaker Isco and Chelsea defender Cesar Azpilicueta in their squad but there was no place for Swansea City midfielder Michu or striker Fernando Torres.
Uruguay have taken a battering recently, losing 4-0 away to Colombia, 4-1 in Bolivia and 3-0 in Argentina in the South American World Cup qualifiers since September.