At the Autodromo Enzo e Dino Ferrari, the 32-year-old driver of Peugeot #7 came in ahead of Marcel Faessler in Audi #1 and Stephane Sarrazin in Peugeot #8.
Allan McNish in Audi #2 was fourth.
"The competition continues between us," Davidson told the Le Mans website afterwards. "It's always good to start from pole position but the race is not only long but also with traffic on the track, you have to survive.
"Our goal at the end of this round is to increase our lead in the rankings of the ILMC (Peugeot has 103 points against 69 to Audi) and starting from the front line will help."
The race starts on Sunday at 11am UK time and is live on British Eurosport.
1. Anthony Davidson (Peugeot Sport Total): 1:31.736
2. Marcel Faessler (Audi Sport Team Joest): +0.618
3. Stephane Sarrazin (Peugeot Sport Total): +0.996
4. Allan McNish (Audi Sport Team Joest): +1.238
5. Guillaume Moreau (Oak Racing): +3.010
6. Neel Jani (Rebellion Racing): +3.311
7. Andrea Belicchi (Rebellion Racing): +3.964
8. Emmanuel Collard (Pescarolo Team): +4.260
9. Maximo Cortes (MIK Corse): +4.348