Developing　alternative　two-dimensional　(2D)　metallic/semiconducting　(M/S)　van　der　Waals　heterostructures　(vdWHs)　along　with　an　understanding　of　interfacial　photocarrier　behavior　is　crucial　for　designing　high-performance　optoelectronic　devices.　Here,　we　comprehensively　explored　the　photophysical　model　of　photocarrier　generation　and　interfacial　transfer　in　as-grown　2D　1T′/2H　MoS2　vdWHs　using　various　spectroscopic　characterizations.　We　demonstrated　the　transitions　of　activated　photocarrier　transfer　trajectories　by　tuning　the　pump　photon　energies　across　the　2H　MoS2　bandgap.　The　importance　of　confined　bilayer　transfer　systems　and　strong　interlayer　coupling　at　vdW　interfaces　for　transfer　efficiency　was　elucidated.　Additionally,　the　fluorophlogopite　substrate　was　found　to　be　an　external　method　for　regulating　photocarrier　generation　in　individual　2H　layers　through　the　p-doping　effect　at　the　substrate-2H　layer　interfaces,　and　this　influence　was　alleviated　after　introducing　the　2H-1T′　vdW　interface.　Particularly,　1T′　MoS2　as　a　broadband　hot　carrier　absorber　enabled　the　ultrafast　(∼133　fs)　injection　and　extraction　of　energetic　hot　carriers　into　the　2H　layer　via　a　photothermionic　emission　mechanism,　achieving　a　high　efficiency　of　∼41%　under　900　nm　photoexcitation　at　room　temperature.　Our　work　offers　fundamental　insights　into　the　complex　interfacial　carrier　photophysics　in　2D　M/S　vdWHs,　providing　a　way　of　constructing　advanced　multifunctional　devices　by　using　these　emerging　materials　as　active　components　and　interface　engineering.　©　2024　American　Chemical　Society.