CO2　conversion　with　pure　H2O　into　CH3OH　and　O-2　driven　by　solar　energy　can　supply　fuels　and　life-essential　substances　for　extraterrestrial　exploration.　However,　the　effective　production　of　CH3OH　is　significantly　challenging.　Here　we　report　an　organozinc　complex/MoS2　heterostructure　linked　by　well-defined　zinc-sulfur　covalent　bonds　derived　by　the　structural　deformation　and　intensive　coupling　of　dx　2　-　y2(Zn)-p(S)　orbitals　at　the　interface,　resulting　in　distinctive　charge　transfer　behaviors　and　excellent　redox　capabilities　as　revealed　by　experimental　characterizations　and　firstprinciple　calculations.　The　synthesis　strategy　is　further　generalized　to　more　organometallic　compounds,　achieving　various　heterostructures　for　CO2　photoreduction.　The　optimal　catalyst　delivers　a　promising　CH3OH　yield　of　2.57　mmol　gcat-1　h(-1)　and　selectivity　of　more　than　99.5%.　The　reverse　water　gas　shift　mechanism　is　identified　for　methanol　formation.　Meanwhile,　energy-unfavorable　adsorption　of　methanol　on　MoS2,　where　the　photogenerated　holes　accumulate,　ensures　the　selective　oxidation　of　water　over　methanol.