A process for producing pentaerythritol wherein at least part of a reaction solution which contains pentaerythritol formals is thermally treated in a pH range of 4.5-5.5 at a temperature of 120 DEG -170 DEG C. for 20-120 minutes and the resultant pentaerythritol is separated as crystals. Sodium hydroxide is added to the separated solution to cause sodium formate to crystallize, followed by separation of the crystals. The remaining solution is recirculated to the reaction system for use in the starting reaction solution.
