Hydrogen (H2) has emerged as a sustainable energy carrier capable of replacing/complementing the global carbon-based energy matrix. Although studies in this area have often focused on the fundamental understanding of catalytic processes and the demonstration of their activities towards different strategies, much effort is still needed to develop high-performance technologies and advanced materials to accomplish widespread utilization. The main goal of this review is to discuss the recent contributions in the H2 production field by employing nanomaterials with well-defined and controllable physicochemical features. Nanoengineering approaches at the sub-nano or atomic scale are especially interesting, as they allow us to unravel how activity varies as a function of these parameters (shape, size, composition, structure, electronic, and support interaction) and obtain insights into structure–performance relationships in the field of H2 production, allowing not only the optimization of performances but also enabling the rational design of nanocatalysts with desired activities and selectivity for H2 production. Herein, we start with a brief description of preparing such materials, emphasizing the importance of accomplishing the physicochemical control of nanostructures. The review finally culminates in the leading technologies for H2 production, identifying the promising applications of controlled nanomaterials.