Carbon materials can be readily prepared from wood derivatives, monosaccharaides such as pentose/hexose and/or polysaccharides in addition to many starting materials by treatment of thermal, chemical and hydrothermal methods. Here, the porous carbon (PC) particles were prepared by removal of silica particles from previously prepared carbon-silica composites by hydrothermal and carbonization process from sucrose. Then, PC particles were modified with polyethyleneimine (PEI) to prepared amine functionalized PC-PEI particles and protonated with hydrochloric acid, PC-PEI+. Finally, these prepared carbon-based particles were used as catalyst for H2 release from NaBH4 methanolysis and PC-PEI+ was found as the most effective catalyst at 25 °C with 4040 ± 126 mL H2. min−1.g−1 HGR value. The Ea value of 23.9 kJ/mol in H2 release reaction from NaBH4 methanolysis catalyzed by PC-PEI+ that is comparable and/or better than most of studies reported in literature. The activity% of PC-PEI+ catalyst was 72% after fifth consequential runs. Additionally, the regeneration ability of PC-PEI+ catalyst was also shown that after fifth regeneration process, there is only 5% decrease in activity%.