The hydrogen evolution via alcoholysis reaction of sodium borohydride with an H3BO3 catalyst was carried out for the first time. In the process of methanol and NaBH4 (NaBH4-MR), the effects of the H3BO3 and NaBH4 concentration, and temperature parameters were examined and evaluated. The hydrogen yields by the NaBH4-MR, NaBH4 ethanolysis (NaBH4-ER) and NaBH4 hydrolysis reactions (NaBH4-HR) with 0.2 M H3BO3 catalyst are 99, 62, and 88% compared to the theoretical hydrogen yield, respectively. The completion times of the NaBH4-MR using the H3BO3 concentrations of 0.2, 0.4, 0.5, 1 M, and saturated acid solution were about 50, 15, 10, 2 and 1 min, respectively. The hydrogen yields obtained with 50, 15, 10, 2, and 1 min for the same acid concentration values were about 100% compared to the theoretical hydrogen value. By increasing the H3BO3 concentration from 0.2 M to the saturated H3BO3 concentration, the completion time of this NaBH4-MR process was reduced by approximately 50 times, resulting in a significant result. The activation energy (Ea) of the NaBH4-MR with the H3BO3 catalyst was 57.3 kJ/mol. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.