Scolari's reign at the London club ran from July 2008 until February 2009 before he was sacked by billionaire Russian owner Roman Abramovich following a poor run of form.
Even though Brazil's side could contain Chelsea's Brazilian trio David Luiz, Ramires and Oscar, Abramovich will doubtless be cheering on his countrymen in the first international to be staged at the ground for 67 years.
Scolari, despite saying last week that performances are more important than results, would be delighted with a win.
The 64-year-old, who led Brazil to victory in the 2002 World Cup, was reappointed coach in November and tasked with the responsibility of winning the trophy again on home soil next year.
Scolari's two opening matches have failed to produce a win, Brazil losing 2-1 to England in London six weeks ago and drawing 2-2 with Italy in Geneva on Thursday after leading 2-0 at halftime.
"For me there was more progress than anything else," he said after Thursday's game.
"We are still implanting a style of play. I liked the team in every aspect, in the way it conducted itself."
He is trying to test as many players as possible before the Confederations Cup starts against Japan in Brasilia on June 15 and only has a handful of games to blend a side capable of winning the competition.
It is already clear Scolari is taking Brazil down a more physical path than predecessor Mano Menezes.
Menezes had begun playing with a 'false number nine' like world champions Spain but Scolari has instead picked Fred, an old-fashioned number nine who has scored in both his matches in charge.
The other big question is whether there is room for Ronaldinho or Kaka.
Ronaldinho had a poor game when he was recalled against England while Kaka had only 20 minutes against Italy and did not look too impressive either.
Oscar, who has been likened to a young Kaka, could well get the nod on his home ground.
Including the last two matches under Menezes, Brazil have gone four games without a win and face a Russian side who have won all four of their World Cup Group F qualifiers and are on course to reach next year's finals.
The Russians arrive in frustrated mood after their qualifier against Northern Ireland in Belfast was postponed on Friday because of heavy snow and continuing bad weather meant Saturday's rescheduled fixture was also scrapped.
Coach Fabio Capello also knows Stamford Bridge well following his four-year spell in control of England and could give several newcomers their debuts against the five-times world champions.
The Italian is expected to keep faith with first-choice goalkeeper Igor Akinfeyev and is likely to pair Dynamo Moscow's Alexander Kokorin with misfiring Zenit St Petersburg striker Alexander Kerzhakov.
The 26-year-old Akinfeyev will hope to extend his country's all-time record, including the Soviet Union era, by keeping a clean sheet for the 10th consecutive international.
Former Chelsea defender Yuri Zhirkov is also likely to feature for the Russians.
Under Capello, Russia are unbeaten in seven matches including friendlies.
Monday's game will be the first international at Stamford Bridge since May 1946 when 75,000 fans saw England beat Switzerland 4-1 in one of several games played as unofficial 'Victory Internationals' following the end of World War Two.
Russia's visit also evokes memories of one of the most famous friendlies played in England when Moscow Dynamo drew 3-3 with Chelsea in front of another huge crowd, estimated at around 100,000 at Stamford Bridge, six months after the war.
Brazil: Julio Cesar; Dani Alves, David Luiz, Thiago Silva, Filipe Luis; Fernando, Hernandes, Kaka or Oscar; Neymar, Fred, Hulk.
Russia: Igor Akinfeyev; Alexander Anyukov, Sergei Ignashevich, Vasily Berezutsky, Andrei Yeshchenko; Yuri Zhirkov, Roman Shirokov, Igor Denisov, Vladimir Bystrov; Alexander Kerzhakov, Alexander Kokorin.