In this study, it is aimed to investigate hydrogen (H2) generation from sodium borohydride (NaBH4) hydrolysis by multi-walled carbon nanotube supported platinum catalyst (Pt/MWCNT) under various conditions (0–0.03 g Pt amount catalyst, 2.58–5.03 wt % NaBH4, and 27–67 °C) in detail. For comparison, carbon supported platinum (Pt/C) commercial catalyst was used for H2 generation experiments under the same conditions. The reaction rate of the experiments was described by a power law model which depends on the temperature of the reaction and concentrations of NaBH4. Kinetic studies of both Pt/MWCNT and Pt/C catalysts were done and activation energies, which is the required minimum energy to overcome the energy barrier, were found as 27 kJ/mol and 36 kJ/mol, respectively. Pt/MWCNT catalyst is accelerated the reaction less than Pt/C catalyst while Pt/MWCNT is more efficient than Pt/C catalyst, they are approximately 98% and 95%, respectively. According to the results of experiments and the kinetic study, the reaction system based on NaBH4 in the presence of Pt/MWCNT catalyst can be a potential hydrogen generation system for portable applications of proton exchange membrane fuel cell (PEMFC).