In　this　work,　we　report　an　in　situ　construction　of　single-site　Ti　active　centers　on　a　carbon　nitride　surface　during　photocatalytic　processes　for　one-pot　chemoselective　hydrogen　transfer　reduction　of　nitroaromatics　and　domino-type　reaction　using　Cp2TiCl2and　-OH-enriched　carbon　nitride　(OHCN)　as　precatalysts.　Due　to　the　selective　adsorption　of　nitro　and　the　promotion　of　photogenerated　charge　transfer　by　single-site　Ti　active　species　and　the　formation　of　Ti3+,　the　system　can　achieve　an　efficient　chemoselective　reduction　of　nitroaromatics　containing　various　substituents,　especially　sensitive　substituents　(CC,　CC,　CO,　CN,　CN,　C-X　(X　is　halogen),　etc.).　The　two　processes　of　chemoselective　reduction　of　nitroaromatics　and　oxidation　of　aromatic　alcohols　are　photocatalytically　coupled　to　form　a　complete　photocatalytic　cycle,　which　allows　the　simultaneous　formation　of　two　high-value-added　products,　aromatic　amines　and　aromatic　aldehydes.　More　valuable　products　like　imines　are　obtained　by　effecting　the　reduction　of　the　nitro　moiety　to　-NH2in　the　presence　of　aromatic　alcohols　that　can　react　in　a　domino-type　process.　This　work　guides　the　in　situ　preparation　of　non-noble　metallic　single-site　photocatalysts　and　provides　a　strategy　for　the　photocatalytic　synthesis　of　valuable　organic　compounds　from　nitroaromatics.　©　2022　American　Chemical　Society.　All　rights　reserved.