To easily obtain the subject compound at a low cost by reacting pentaerythritol with a specific compound in the presence of a specific catalyst and completely esterifying four hydroxyl groups of pentaerythritol.

A pentaerythritol tetraester of formula II is obtained by reacting (A) pentaerythritol of formula I with (B) a compound of the formula; R1COOR2 (R1 is an alkyl; R2 is H or an alkyl), a compound of the formula; R1COCl or a compound of the formula; (R1CO)2O in the presence of (C) a catalyst consisting of a compound of the formula; [N(Tf)2]n [Tf is SO2Rf (Rf is F, a lower perfluoroalkyl); M is an alkali metal, an alkaline earth metal, a rear earth element, a transition metal, Al, Si, etc.; (n) is an integer expressing the valency of M] or a compound of the formula; HN(Tf)2. For 1 mole of the ingredient A, ≥4 mole, preferably 4-8 mole of the ingredient B is used. For the ingredient A, 0.01-50 mole %, preferably 1-20 mole % of the ingredient C is used.