The theoretically predicted volcano plot for hydrogen production shows the best catalyst as the one that ensures that the hydrogen binding step is thermodynamically neutral. However, the experimental realization of this concept has suffered from the inherent surface heterogeneity of solid catalysts. It is even more challenging for molecular catalysts because of their complex chemical environment. In this presentation, I report that the thermoneutral catalyst can be prepared by simple doping of a platinum atom into atomically precise gold nanoclusters such as Au₂₅(SR)₁₈ and Au₃₈(SR)₂₄, where SR is a thiolate ligand. The catalytic activity of the resulting bimetallic nanocluster for the hydrogen production is found to be significantly higher than reported catalysts. It is even better than the benchmarking platinum catalyst. The bimetallic metal nanoclusters represent a new class of catalysts that bridge homogeneous and heterogeneous catalysis and provide a platform for the discovery of finely tuned catalysts for hydrogen production from water. Studies of electrocatalysis by the bimetallic nanoclusters provide many important design principles for the development of electrocatalysts with tailored cluster structure and adsorption energy. These principles are illustrated with nanocluster-based electrocatalysts for water splitting and CO₂ conversion.