Reaction intermediates PCP/BZA (PBI) and tetramethylene bis(orthophosphate) (TBOP) wer synthesized from polycaprolactone (PCP) and benzoic acid (BZA) and from pyrophosphoric acid and 1,4-butanediol, respectively. Benzoic acid modified polyesters containing phosphorus (APTB-5, -10, -15) were synthesized by polycondensation of the prepared PBI (containing 5, 10, 15wt% of benzoic acid), TBOP, adipic acid, and 1,4-butanediol. The structure and characteristics of APTBs were examined using FT-IR, NMR, GPC, and TGA analysis. The increase of the amount of BZA in the synthesis of APTBs resulted in decrease in average molecular weight and kinematic viscosity. From the TGA analysis of APTBs, it was found that the afterglow decreased with the amount of BZA content at the high temperatures.