Hydrogen evolution reaction (HER) is known as the heart of various energy storage and conversation systems of renewable energy sources. Here we observe the cluster reactions of a light transition metal, vanadium, with water in a gas-phase flow tube reactor. While HER products of V1 and V2 were not observed, the effective HER of water on neutral Vn (n ≥ 3) clusters reveals reasonable and size-dependent reactivity of the vanadium clusters. Superatomic features and reaction dynamics of V10, V13, and V16 are highlighted. Among the three typical superatoms, V10 and V16 exhibit an abnormal superatomic orbital energy level order, 1S|2S|1P|1D..., where the energy-reduced 2S orbital helps to accommodate the geometric structure and hence reinforce the cluster stability. In comparison, V13 bears a less symmetrical structure and reacts readily with water, allowing for recombination of a hydroxyl atom with an adsorbed hydrogen atom, akin to a fishing-mode HER process. The joint experimental and theoretical study on neutral Vn clusters clarifies the availability of superatom chemistry for transition metals and appeals further development of cluster theory based on electronic cloud/orbital analysis instead of simply counting the valence electrons. Also, we provide insights into the HER mechanism of metal clusters and propose a strategy to design new materials for portable fuel cells of hydrogen energy.