Titanates are widely used in the synthesis of polyesters, such as Poly (butylene succinate) (PBS), due to their excellent catalytic activity for polycondensation. However, the hydrolysis sensitivity of titanate and side reactions at high temperatures restrict the further improvement of the molecular weight of polyesters and lead to the high content of end carboxyl group content in the products. In this work, we prepared titania–silica composite aerogels with resistance to hydrolysis and large specific surface area, which were further explored as an efficient catalyst for polycondensation reactions. A series of titania–silica composite aerogel catalysts for PBS polycondensation were successfully prepared by the sol-gel method. The influence of a Ti/Si ratio on the surface morphology and structure of the aerogels was examined. Titania–silica composite aerogel exhibits the surface characteristics of high specific surface area and high Lewis acid content. The specific surface area of titania–silica composite aerogels can reach 524.59 m2/g, and the Lewis acid content on the surface can reach 370.29 μmol/g. Furthermore, the catalytic performance for the polycondensation reaction of PBS was investigated. The intrinsic viscosity of PBS synthesized by catalysis with the composite catalyst with a Ti/Si ratio of 9/1 reaches 1.74 dL/g, with the Mnof 7.72 × 104g/mol. The hydrolysis resistance stability of the titania–silica composite aerogel is greatly improved compared with traditional tetrabutyl titanate (TBT), and the end carboxyl group content of PBS is effectively reduced to lower than 30 mol/ton.