Metallic tungsten disulfide (WS2) monolayers have been demonstrated as promising electrocatalysts for hydrogen evolution reaction (HER) induced by the high intrinsic conductivity, however, the key challenges to maximize the catalytic activity are achieving the metallic WS2 with high concentration and increasing the density of the active sites. In this work, single-atom-V catalysts (V SACs) substitutions in 1T-WS2 monolayers (91% phase purity) are fabricated to significantly enhance the HER performance via a one-step chemical vapor deposition strategy. Atomic-resolution scanning transmission electron microscopy (STEM) imaging together with Raman spectroscopy confirm the atomic dispersion of V species on the 1T-WS2 monolayers instead of energetically favorable 2H-WS2 monolayers. The growth mechanism of V SACs@1T-WS2 monolayers is experimentally and theoretically demonstrated. Density functional theory (DFT) calculations demonstrate that the activated V-atom sites play vital important role in enhancing the HER activity. In this work, it opens a novel path to directly synthesize atomically dispersed single-metal catalysts on metastable materials as efficient and robust electrocatalysts.