Steam reforming for hydrogen production is one of the important research directions for clean energy. NiTiO₃ catalysts with a hierarchical porous structure are prepared and applied to methanol steam reforming for hydrogen production. The results show that the optimum catalyst (10% Ni–Ti–O_x) not only has a hierarchical porous structure, but it also involves the coexistence of NiTiO₃, anatase TiO₂ and rutile TiO₂. The formation of NiTiO₃ is beneficial to the adsorption and activation of methanol molecules on the surface of the Ni–Ti–O_x catalyst, and the main intermediate species of the methanol molecular reaction are hydroxyl groups, methoxy species and formic acid species. Furthermore, the methanol steam reforming reaction is mainly dominated by methanol decomposition at low temperature (350–500 °C), while it is mainly dominated by methanol and water molecular reactions at high temperature (500–600 °C).