The　selective　degradation　of　specific　substances　in　mixed　contaminants　is　quite　challenging.　And　a　general　approach　for　sensitized　oxide　semiconductor　relies　on　dip-coating　method　with　sensitizer.　Here,　hydrophilic　2D,　nest-like　architecture　ZnO　(ZnO　NA)　was　hydrophobicly　functioned　by　monomolecular–layer　tetraphenylporphyrin　zinc　(ZnTPP),　where　ZnTPP　was　synthesized　by　means　of　an　in　situ　center-substituted　(ISCS)　process.,　i.e.,　the　hydrogen　atoms　in　the　core　of　metal-free　tetraphenylporphyrin　(H　2　TPP)　are　substituted　by　the　unsaturated　zinc　ions　in　ZnO　NAs.　ZnTPP/ZnO　NA　was　exhibited　with　significant　hydrophobicity,　benefitting　to　absorb　hydrophobic　phenol　(PL).　Further,　it　is　realized　to　selectively　photodegradate　PL　in　the　mixture　by　ZnTPP/ZnO　NAs　under　visible　irradiation.　Note　that　the　rate　of　degradation　to　hydrophobic　PL　by　ZnTPP/ZnO　NA　is　9.17　times　of　that　for　ZnO　NA　within　150　min;　on　the　contrary,　the　degradation　rate　of　hydrophilic　rhodamine　B　(RhB)　by　ZnTPP/ZnO　is　reduced　by　40%.　Radiative　lifetime　of　photogenerated　charges　is　obviously　increased　by　ZnTPP/ZnO　NA　compared　with　that　of　ZnTPP,　indicating　the　effective　charge　separation　for　ZnTPP/ZnO　NAs.　In　addition,　ZnTPP/ZnO　NA　produced　more　superoxide　radicals　(·O　2　−　)　in　comparison　to　ZnO　NA.　With　surface　functionalization,　the　feasibility　of　selective　photocatalysis　under　visible　irradiation　is　demonstrated.　©　2019　WILEY-VCH　Verlag　GmbH　&　Co.　KGaA,　Weinheim