Styrene/Sodium allyl sulfonate copolymer (St-c-SAS) were prepared using soap-free emulsion polymerization method and boiling at high-speed stirring, and it was acided to obtain an efficient, stable, reusable new solid acid catalyst styrene/acrylic acid copolymer (St-c-AS). Elemental analysis and acid–base titration techniques showed that St-c-AS have high concentration of sulfonic groups. Differential thermal analysis (DTA) and thermogravimetric analysis (TG) results showed that the sulfonic of copolymer was hard to fall off at high temperature. Esterifications of acetic acid with ethanol showed that St-c-AS has high catalytic activity, and the catalyst can be reused without separation of 10 times, the esterification yields close to or exceed 100%. The superior performance of St-c-AS is attributed to their unique features including large surface area, high content of sulfonic groups as well as high temperature resistance.