In this study, orange peel (OP), one of the organic wastes, was first used as a metal-free catalyst for the production of hydrogen from sodium boron hydride (NaBH 4 ). In order to prepare an orange peel catalyst (OP–H 3 PO 4 -Cat) with the best catalytic activity, experiments were carried out on pure orange peel with different acid types, different burning temperatures and different burning times. As a result of these experiments, it was determined that OP-H 3 PO 4 -Cat treated with 30% H 3 PO 4 and burned at 400 °C for 45 min had the best catalytic activity. The OP-H 3 PO 4 -Cat material was characterised by several techniques such as FTIR, XRD and SEM. As a result, the hydrogen generation rates (HGR) at 30 °C and 60 °C in the methanolysis reaction of 2.5% NaBH 4 catalysed by OP-H 3 PO 4 -Cat were found as 45,244 and 61,892 mLmin −1 g.cat −1 , respectively. The activation energy of OP-H 3 PO 4 -Cat catalyst was calculated as 12.47 kJmol -1 . • Orange peel was used as a metal-free catalyst for the first time. • Environmentally friendly metal-free catalyst for the generation of H 2 with low Ea. • This metal-free catalyst exhibits extremely high hydrogen generation rate.