The figure for Luíz, 27, would represent a world record for a defender and trump the £36m PSG paid AC Milan for Thiago Silva two years ago. Silva and Luíz will start at centre-back for Brazil at the World Cup, and the latter will likely dislodge compatriot Alex at the Parc des Princes.
A year ago, Luíz was the subject of a failed bid from Barcelona and was also interesting Bayern Munich, however he will be the first victim of José Mourinho's squad cull as he begins to mould his second major Chelsea side.
Luíz played both games against PSG in the Champions League quarter-finals
Chelsea could make a £16.5m profit on Luíz, who they bought from Benfica three years ago, despite the Brazilian struggling to adapt to his defensive role in the Premier League. Memorably described by Sky Sports pundit Gary Neville as a player "controlled by a 10-year-old on a PlayStation", he was untrusted by Mourinho in central defence as John Terry and Gary Cahill formed an impressive partnership last season.
Luíz was, invariably, deployed in a defensive midfield role but enjoyed his best spell in the Chelsea team during Rafael Benítez's six interim months. Signed when Carlo Ancelotti was manager, Luíz has played under five managers in three-and-a-half seasons at Stamford Bridge.
Oscar, another Brazilian, could follow Luíz out of west London, while Samuel Eto'o is unlikely to sign a new deal with Chelsea after he labelled Mourinho a "fool" and a "puppet". John Obi Mikel, along with Luíz, has suffered from the imposing Nemanja Matić's arrival.
Ashley Cole has already confirmed he will leave Chelsea, and Atlético Madrid's Filipe Luis and Sevilla’s Alberto Moreno are both highly regarded by Mourinho as he seeks a replacement left-back.