Hybrid layered materials assembled from atomically thin crystals and small molecules bring great promises in pushing the current information and quantum technologies beyond the frontiers. We demonstrate here a class of layered valley-spin hybrid (VSH) materials composed of a monolayer two-dimensional (2D) semiconductor and double-decker single molecule magnets (SMMs). We have materialized a VSH prototype by thermal evaporation of terbium bis-phthalocyanine onto a MoS2 monolayer and revealed its composition and stability by both microscopic and spectroscopic probes. The interaction of the VSH components gives rise to the intersystem crossing of the photogenerated carriers and moderate p-doping of the MoS2 monolayer, as corroborated by the density functional theory calculations. We further explored the valley contrast by helicity-resolved photoluminescence (PL) microspectroscopy carried out down to liquid helium temperatures and in the presence of the external magnetic field. The most striking feature of the VSH is the enhanced A exciton-related valley emission observed at the out-of-resonance condition at room temperature, which we elucidated by the proposed nonradiative energy drain transfer mechanism. Our study thus demonstrates the experimental feasibility and great promises of the ultrathin VSH materials with chiral light emission, operable by physical fields for emerging opto-spintronic, valleytronic, and quantum information concepts.