Heterogeneous Brønsted solid acid catalysts have the potential to decrease the environmental impact related to chemical production. Herein, we have synthesized polyvinyl bound trisulfonate ethylamine chloride (PV-THEAC) and polyvinyl bound disulfonate ethylamine (PV-DSEA) as Brønsted solid acid catalysts which exhibited effective catalytic activity for acid catalyzed glycosylation reactions with sugar derivatives. In particular, 0.3 equiv. of the PV-THEAC catalyst was found to be the most efficient and a reusable catalyst for glycosylation reactions. A high density of the trisulfonic group (–OSO₃H) contributed to the excellent catalytic activity during glycosylation. Moreover, glycosylation reactions with D-mannose, D-xylose and D-glucose have been studied with alcohol. Remarkable acceleration of the glycosylation reaction using a glycosyltrichloroacetimidate donor was obtained with the selective production of β-glycoside.