The Blues are believed to have identified the France international as a priority target to beef up their depleted defence ahead of the 2022-23 season.
Kimpembe and Marquinhos formed PSG's first-choice centre-back pairing last season, with Sergio Ramos often consigned to the treatment room with various injury problems.
Kimpembe registered two goals and one assist in 41 appearances across all competitions for PSG last term, including 29 starts in their triumphant Ligue 1 campaign.
The 26-year-old also captained the side on a number of occasions under Mauricio Pochettino, and he only has two years left to run on his contract at the Parc des Princes.
Kimpembe worked under Chelsea boss Thomas Tuchel during the German's time in charge of PSG, but the Blues will not be able to sign the centre-back on the cheap.
According to The Independent, PSG have set a €50m (£42.3m) asking price on Kimpembe, and the French champions would want the deal to rise to as much as €60m (£50.8m) with add-ons.
The report adds that PSG - who are now the firm favourites to sign Milan Skriniar from Inter Milan - would be open to a sale should Chelsea match their valuation.
However, Chelsea are supposedly still falling short of PSG's asking price by about €20m (£17m), and talks between the two clubs will continue before the Blues table their first bid.
Kimpembe has risen through the youth ranks at PSG since joining their academy in 2005 and has now registered three goals and two assists in 220 first-team games for the capital club.
The France international has won six Ligue 1 titles, five Coupe de France crowns, four Coupe de la Ligues and five Trophee des Champions honours during that time and was also part of the triumphant France squad during the 2018 World Cup.
While Chelsea are struggling to meet PSG's valuation of Kimpembe, the Blues are now understood to be on the verge of sealing a move for Napoli's Kalidou Koulibaly.
The Senegal international is reportedly due to undergo his medical on Thursday after Chelsea agreed a £33.8m deal to sign him from Luciano Spalletti's side.
Tuchel has lost Andreas Christensen and Antonio Rudiger to Barcelona and Real Madrid respectively this summer, and the club are also said to be working on a deal to re-sign Nathan Ake from Manchester City.
Further up the pitch, Raheem Sterling's move to Chelsea from Man City was confirmed on Wednesday, but the Blues ultimately lost out on the signature of Raphinha to Barcelona.