A novel heterogeneous strong acid catalyst has been synthesized through the copolymerization of p-toluenesulfonic acid and paraformaldehyde with sulfuric acid as catalyst. The novel catalyst owns the strong acidity as much as 4.0 mmol/g, while Nafion and Amberlyst-15 only has the acidity of about 0.8 mmol/g. Furthermore, the catalyst possesses the advantages of the high thermal stability (200 C) and low cost for the simple synthetic procedure. The catalytic activities of the novel catalyst were taken through esterification of acetic acid and ethanol and acetalization of benzolaldehyde and 1,2-ethandiol. The results showed that the novel catalyst showed much higher activities than the Amberlyst-15 and owned even the comparative activity to sulfuric acid, which made the catalyst hold great potential for the replacement of the traditional homogeneous catalyst for the green process.