Methanol steam reforming (MSR) is considered an effective method for hydrogen storage and to generate high-quality hydrogen for fuel cells. In this work, a comprehensive investigation of the methanol steam reforming process using a bimetallic Pt–Rh and Cu–Ni based on different oxide supports is presented. Highly dispersed titania and zirconia doped with indium and niobium ions were synthesized by sol–gel method. The effect of the nature and quantity of the dopant cation (In, Nb) on the catalytic performance of titania supported metal catalysts was investigated. The conclusions obtained show a significant effect of both the metal alloy and the oxide support nature on the activity and selectivity of the methanol steam reforming process. Pt–Rh alloy catalyst shows higher hydrogen yield, but its selectivity in the MSR process is lower than for the catalysts containing the Cu0.8-Ni0.2 alloy. Heterovalent indium doping of titania leads to the catalytic activity increase. It was suggested that this is due to the defects formation in the oxygen TiO2 sublattice. On the contrary, the use of niobium oxide as a dopant decreases the catalyst activity in the methanol steam reforming process but leads to the selectivity increase in the studied process.