The macroporous phenol-furfural sulfonic acid resin catalyst (PFuSR) was prepared. The resin was characterized by chemical analysis, thermal analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, and reactions of esterification. There exist in PFuSR different kinds of acidic groups such as -OH, -COOH, and -SO3H. The catalytic relative activity of PFuSR in the reaction of acetic acid and n-butanol is 104 times that of macroporous polystyrene sulfonic acid resin D72. Thermal analysis showed that PFuSR did not begin to desulfonate until temperatures of 220 degreesC were reached. The resin is suitable for use continually up to 200 degreesC, verified by successfully performing the reaction of maleic anhydride with 2-ethyl-1-hexanol to form di-2-ethylhexyl maleate.