In this study, a novel microalgae based support material was developed and applied. The Chlorella Vulgaris microalgal strain was modified by treating the algal biomass with phosphoric acid for proton binding process (CVMS-H3PO4). Ultimately, the CVMS-H3PO4-metal (Cu-B, Ni-B, or Fe-B) catalysts were used as highly efficient solid catalysts to produce hydrogen from the methanolysis of NaBH4. Once the superior metal was identified, the NaBH4 concentration, metal percentage in the supported-catalyst, catalyst amount, and temperature effect on the methanolysis reaction was thoroughly investigated. The maximum hydrogen production rate for the CVMS-H3PO4 supported-catalyst was obtained with the use of 20% Cu metal at 30 degrees C and it was found to be 6500 mL/min/g(cat). In addition, the maximum hydrogen production rate for the CVMS-H3PO4 supported-catalyst was attained with the use of 20% Cu metal at 60 degrees C and it was found to be 21176 mL/min/g(cat). Also, the activation energy was determined as 23.79 kJ/mol. The re-usability studies of the microalgal strain supported-Cu-B catalyst were performed and it was found that there was no decrease in % conversion for this catalyst. XRD, FTIR, SEM, and ICP-MS analysis were carried out to characterize CVMS-H3PO4-CuB catalyst thoroughly. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.