The　photo-degradative　selectivity　for　a　photocatalyst　is　strongly　dependent　to　the　specific　interaction　between　the　photocatalyst　and　substrate.　Here,　a　hydrophilic　functional　molecule,　tetrasulfonate　substituted　phthalocyaninatozinc　(II)　(ZnTSPc)　was　modified　on　the　two　dimensional　(2D)　surface　of　ZnO　via　an　on-surface　synthesis.　In　the　synthetic　process,　the　dangling　bonds　of　zinc　ions　on　the　high　active　facet　((001)　and　(100))　of　dumbbell-like　ZnO　(ZnO　ZDs)　were　used　as　a　template　of　cyclotetramerization　reaction　for　ZnTSPc　by　an　on-surface　process,　where　4-(potassium　sulfonate)　phthalonitrile　was　used　as　a　precursor.　Compared　with　pure　ZnTSPc,　a　significant　fluorescence　quenching　(96.3　%)　for　ZnTSPc/ZnO　happened.　The　photogenerated　electron-hole　pairs　were　effectively　separated　by　photoexcited　electrons　injecting　from　ZnTSPc　into　ZnO　ZDs　conduction　band　with　a　rapid　charge　transfer　rate　(6.1　×　107s−1).　Under　visible　light　irradiation,　ZnTSPc/ZnO　as　a　photocatalyst　illustrates　higher　catalytic　degradation　rate　for　both　phenol　(PL)　and　methylene　blue　(MB)　than　those　by　using　ZnO　ZDs.　Due　to　the　hydrophilicity　of　sulfo　groups　on　the　peripheral　substituted　ZnTSPc,　MB　as　a　hydrophilic　dye　had　strong　attraction　towards　super-hydrophilic　ZnTSPc/ZnO　via　π-π　conjugation,　but　PL　with　hydrophobicity.　The　relative　degradation　rate　of　MB　by　using　ZnTSPc/ZnO　is　4.19　times　faster　than　that　of　PL,　illustrating　ZnTSPc/ZnO　with　distinct　photocatalytic　selectivity　under　visible　irradiation.　The　energy-band　feature　and　mechanism　for　photoexcited　electrons　transition　are　illustrated　based　on　electrochemical　analysis.　©　2020　Elsevier　B.V.