Andy Murray will play Jeremy Chardy of France in his opening match at the Paris Masters on Wednesday.
The Briton, seeded second has won all three previous matches against world number 104 Chardy.
World number one Novak Djokovic and third seed Roger Federer are also on the schedule on Wednesday.
The eight-man field for the ATP World Tour Finals will be confirmed in Paris, with three spots up for grabs.
Play on Wednesday gets underway at 0930 GMT, with Murray playing Chardy in the second match on Central Court before Djokovic takes on Ivan Dodig, and Federer then plays Adrian Mannarino.
Djokovic has been a major doubt for Paris with a shoulder injury but he practised at the Bercy arena on Tuesday evening, and the Serbian is in line to collect a $1.6m bonus from ATP if he plays as he will have appeared at seven of the year's eight mandatory Masters 1000 events.
The 24-year-old withdrew from Shanghai last month because of the shoulder injury.
Murray was forced to pull out of last week's Basle tournament with a leg injury but he returned to action on Monday evening to team up with Ross Hutchins and beat Nicolas Almagro and David Marrero in the doubles.
The Scot, 24, is on a 16-match winning streak in singles after taking the titles in Bangkok, Tokyo and Shanghai.
Nadal withdrew from Paris in order "to prepare well for the end of this season and also for 2012", with both the Tour Finals and Davis Cup final against Argentina to come in the next month.
The end-of-season Tour Finals showpiece begins at London's O2 Arena on 20 November, with Tomas Berdych, Jo-Wilfried Tsonga and Mardy Fish strong favourites to secure the remaining places.
Djokovic, Nadal, Murray, Federer and David Ferrer are already confirmed for London.
Meanwhile, Jamie Murray and Colin Fleming secured an impressive victory over Feliciano Lopez and Fernando Verdasco in round one of the doubles on Tuesday.
The British pair beat their Spanish opponents 6-1 2-6 10-8 to set up a second-round meeting with seventh seeds Rohan Bopanna and Aisam-Ul-Haq Quereshi.