David Luiz did not train with the Chelsea first-team on Wednesday, and is seeking to force a surprise transfer to Arsenal.
The Brazilian only signed a new two-year deal at Stamford Bridge in May, a break from Chelsea's policy of only handing over-30s one year contracts.
However, just 24 hours before Thursday's transfer deadline, Luiz is pushing for a move.
The veteran centre-back did not start Chelsea's final pre-season fixture against Borussia Monchengladbach - Kurt Zouma and Andreas Christensen were preferred - and will be fourth choice under Frank Lampard when Antonio Rudiger returns to fitness.
As such, amid increasing interest from the Gunners, who have failed to land either Daniele Rugani or Dayot Upamecano, Luiz wants to reunite with Unai Emery.
The Arsenal boss and Luiz have worked together before, briefly, at PSG.
And despite being sold just two months into the Spaniard's reign at the Parc des Princes, Emery left quite the impression on the 32-year-old.
Speaking ahead of the Europa League final between the two clubs in May, Luiz was full of praise for the Arsenal boss.
"Unai came [to Arsenal ] to try to build a new philosophy and to try to gain the trust of the players, from the fans, from the club," Luiz declared. "I think he has been doing an amazing job.
“I had the opportunity to work with Unai for a few months. He’s a great guy, a great coach, a great person.
"He’s passionate. He loves his work. He likes to build teams who are spirited, play with passion and you can see that.
"He has had the opportunity to work with a lot of young players and I think they have understood his philosophy."
PSG's sale of Luiz in 2016 was largely predicated on Marquinhos' emergence as first choice alongside captain Thiago Silva.
When Chelsea offered a fee in the region of £34million to take Luiz back to Stamford Bridge, PSG chiefs took the opportunity to sell a player who wanted to return to London.
Gunners boss Emery admitted on Wednesday that, following Laurent Koscielny's acrimonious departure to Bordeaux, he is seeking another experienced centre-back before the close of the window.
"We want our supporters to be happy, to be the best team with the best players," Emery told Sky Sports.
"We tried to sign some important and expensive players for our defence, but we cannot do that and other second line players don’t make us really, really convinced to sign them.
"We have centre-backs, we also have one young one in Dino Mavropanos, with everyone speaking about him and how he can improve, and Rob Holding.
"But if we can in the last day we are going to try to sign another centre-back with the capacity to help us, so we can have a good balance with attacking and defending players."
