Millar, who won the British Championship in the Isle of Man last week, is contracted to the company, who have financial problems and could not offer their support for the three-week event, which starts on Saturday.
The 36-year-old Millar was set to break Barry Hoban's record of 12 rides set in the 1960s and 70s.
Millar, who finished fourth in the 1984 race when he became the first British rider to win the King of the Mountains category, is still some way behind the overall record of 16 Tour rides held by the Dutchman, Joop Zoetemelk.
Le Groupement, who also included the current world champion, Luc Leblanc, in their squad, announced their withdrawal yesterday.
The Tour organisers immediately named the Aki team as replacements. Aki have Poland's Zenon Jaskula, third in 1993, as their top rider.
The absence of Millar and Leblanc deprives the race of two more leading riders after the Latvian Piotr Ugrumov was also ruled out. Ugrumov, runner- up behind Miguel Indurain last year, has failed to recover in time from broken ribs sustained in a fall during the Tour of Switzerland two weeks ago.
Leblanc, suffering from an ankle injury, was forced to abandon the French championship last Sunday after 70km but he had vowed to take part in the Tour to "shut the critics up".