Brazil reached out for its World Cup-winning coach from 2002 after firing Mano Menezes in November, with the national team slipping to a worrying — if slightly misleading — FIFA ranking of No. 18.
Scolari has less than 18 months to turn things around before the country hosts its first World Cup since 1950 — and a win at Wembley Stadium would be a nice start to the repair job he is undertaking with newly appointed technical director Carlos Alberto Parreira, the coach when Brazil won its fourth world title in 1994.
"They know the cultures of the country and the pressures of the job," England manager Roy Hodgson said. "But I reckon Phil and Carlos Alberto will be thinking, 'We could have had an easier start than England at Wembley.' Our job is to make sure they don't get one."
Spain and France meet in a crucial World Cup qualifier next month and they are both preparing for that match with prestigious friendlies on Wednesday.
Spain, the world and European champion, flies out to Doha to play World Cup semifinalist Uruguay while France hosts second-ranked Germany.
In another match between European heavyweights, Italy travels Amsterdam to play the Netherlands. And it could all be about the head-to-head between Lionel Messi and Zlatan Ibrahimovic — two of the best forwards in the world — when Argentina plays away at Sweden.
In terms of prestige, though, nothing can compare to an England-Brazil match at Wembley. It pits the founders of the sport against the game's best ever practitioners and record five-time World Cup winners at the so-called "Home of Football."
"It's going to be a great occasion," said Hodgson, who isn't even a year into his job with sixth-ranked England.
One player in each squad — Ronaldinho for Brazil and Ashley Cole for England — is set to win his 100th international cap should they feature at Wembley. The 32-year-old Ronaldinho's presence is particularly telling.
The former Barcelona and AC Milan forward was overlooked in the final part of the much-maligned Menezes' reign, but has been brought back by Scolari to lead a squad that has been short on experience in recent years. Ronaldinho could be paired in attack with Neymar.
"They are great players and I want them to show what they can do," Scolari said. "Not only on the field, but they also have to show character and attitude. They need to be aware of their responsibility when they are wearing the jersey of the Brazilian national team."
The talent is still there in a Brazil squad also featuring Hulk, Luis Fabiano and Dani Alves and it was widely believed the team was starting to make progress prior to Menezes getting fired, soon after big wins over Iraq (6-0) and Japan (4-0).
The Brazilian football federation said there will be a minute's silence to honour the 235 people who died in nightclub fire in Santa Maria, Rio Grande do Sul, last month.
Carles Puyol is another player who could reach 100 appearances for his country if the Barcelona defender gets a game against Uruguay and its impressive striking partnership of Edinson Cavani and Luis Suarez. Puyol hasn't played for Spain since before last year's European championship, which he missed due to injury.
"I know it is a friendly ... but we have to take this game very seriously," Spain coach Vicente del Bosque said. "It is a team that will serve us well (for preparing for the World Cup qualifiers)."
Spain and France are level on points after three of eight group games, after drawing in Spain in October. The French then went on to beat Italy away in a friendly in November, showing they have the credentials to knock Spain down to a playoff spot in the fight for World Cup qualification.
"It will be a good test for us," France coach Didier Deschamps said of the Germany game. "There's a lot of expectation from the fans after the way we played in Spain and Italy. It's important that the players show the desire on the pitch."
Rennes winger Romain Alessandrini is in line for his international debut, while right back Bacary Sagna could make his first appearance for France since September 2011.
Miroslav Klose needs one goal to equal Gerd Mueller's German record of 68, though the Lazio striker's participation is in doubt after picking up a right knee injury for Lazio.
Germany is being challenged by Sweden in World Cup qualifying and ahead of the resumption of group play in March, the Swedes will test themselves against Argentina and Messi, the four-time world player of the year.
"If you have a dream, which I have, to win a medal in a big championship, it is very important to play these kind of games," Sweden coach Erik Hamren said.
Ibrahimovic's last act in an international game was that stunning overhead kick goal to complete a hat trick in a 4-2 win over England in November, but he'll do well to upstage the prolific Messi on Wednesday.