This chapter provides an overview of the recent advances in the development of metal nanoparticles by using the tools of molecular chemistry. The objective is to illustrate the interest of this synthesis approach through a selection of examples from our group concerning hydrogenation catalysis. We expose here the efforts that allowed reaching metal nanoparticles with specific characteristics and therefore to study the structure–property relationships in a precise manner. We describe how the control of the nanoparticle surface properties by an appropriate choice of the stabilizing ligands impacts in catalytic performances.