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This study presents a method to polymerize aniline in styrene‐divinylbenzene copolymer pores using benzoyl peroxide as an initiator. The composites are sulfonated, impregnated with tin oxide (IV) and used as heterogeneous catalysts in the direct polycondensation synthesis of PLGA. Evaluation of parameters such as molar proportion, temperature, time, quantity and type of catalyst were carried out. The characterization of composites and PLGA's were performed by: elemental analysis, DRX, FTIR, nitrogen adsorption–desorption, Brønsted acid site determination, SEM, ICP/OES, and inherent viscosity. The polyaniline deprotonation before thermal treatment enhances crosslinking, increasing surface area and stability of the porous structure. The composite acts as a catalyst, increasing PLGA molar mass, reducing oxidation and tin contamination. The process has several advantages like PLGA production without solvent contamination, lower tin content, and no high‐cost cyclic dimmers use. So far, the results show promising catalytic performance of the developed composite.