Fir char sulfonic acid was prepared by pyrolysis at 350°C and sulfonation from fir processing residues. FT-IR、XRD and XPS analysis showed that fir pyrocarbon retains the benzene ring structure of lignin, with the active hydrogen for sulfonation. And sulfonic groups successfully bonded with the charcoal skeleton. The catalytic properties of fir char sulfonic acid were investigated in the ring-opening addition reactions of styrene oxide with five alcohols. The results showed that fir char sulfonic acid has good catalytic activity in these alcoholysis reactions. The catalyst is also security, stability and environment friendly.