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The new developed sulfonated solid acid catalyst (SSAC) was prepared by carbonization of palm empty fruit bunches (PEFB) then followed by sulfonation. The sulfonation and acidity functionalization on catalyst was conducted in the presence of 10% hydroxyethylsulfonic acid and acrylic acid (v/v) as co-polymer generated by hydrothermal process at 180°C for 4h in Teflon Stainless Steel Autoclave. The SSAC is providing a good catalytic activity for hydrolysis of cassava peel starch. The hydrolysis performance was investigated by variation of cassava peel concentration and reaction time. The Total reducing sugar (TRS) concentration was achieved about 13.54 mg/mL which obtained by hydrolyzing of 5% (w/v) of cassava peel starch at 100°C for 1 h using 5% (w/v) of SSAC. The SSAC demonstrated good stability with only 6% derivation in TRS concentration after 3 repetitions.