Molecular surfactants are widely used to control low-dimensional morphologies, including 2D nanomaterials in colloidal chemical synthesis, but it is still highly challenging to accurately control single-layer growth for 2D materials. A scalable stacking-hinderable strategy to not only enable exclusive single-layer growth mode for transition metal dichalcogenides (TMDs) selectively sandwiched by surfactant molecules but also retain sandwiched single-layer TMDs' photoredox activities is developed. The single-layer growth mechanism is well explained by theoretical calculation. Three types of single-layer TMDs, including MoS2, WS2, and ReS2, are successfully synthesized and demonstrated in solar H2 fuel production from hydrogen-stored liquid carrier—methanol. Such H2 fuel production from single-layer MoS2 nanosheets is COx-free and reliably workable under room temperature and normal pressure with the generation rate reaching ≈617 µmole g−1 h−1 and excellent photoredox endurability. This strategy opens up the feasible avenue to develop methanol-storable solar H2 fuel with facile chemical rebonding actualized by 2D single-layer photocatalysts.