The　carbon-based　materials　with　metal-N-C　active　sites　have　been　widely　studied　on　the　electrocatalysis　for　carbon　dioxide　reduction　reaction　(CO2RR),　however,　they　were　investigated　a　few　for　the　photocatalytic　CO2RR.　Here,　cobalt　phthalocyanine　(CoPc)　molecules　with　intrinsic　Co-N4-C　moiety　are　successfully　dispersed　on　graphene　oxide　(GO)　as　the　CO2RR　photocatalyst.　The　morphology,　structure,　and　component　of　CoPc/GO　composites　with　the　different　ratio　of　GO　to　CoPc　are　systematically　characterized,　confirming　the　existence　of　Co-O-C　axial　coordination　bond　between　CoPc　and　GO.　The　optical,　photoelectric,　and　electrical　properties　of　CoPc/GO　composites　are　carefully　investigated,　indicating　their　synergistic　role　of　CoPc　and　GO　in　photocatalysis.　With　the　optimal　CoPc/GO　sample　as　photocatalyst,　a　∼1500　μmol⋅g−1⋅h−1　evolution　rate　and　∼　85%　selectivity　of　CO　and　CH4　can　be　achieved,　which　is　much　higher　than　those　performances　of　CoPc.　After　the　reduction　of　CoPc/GO　to　CoPc/rGO,　the　rate　of　CO2RR　to　CO　and　CH4　is　reduced　to　916　μmol⋅g−1⋅h−1,　indicating　the　important　role　of　Co-O-C　axial　bond　in　the　CO2RR.　This　work　provides　a　simple　way　to　prepare　the　single-molecule　catalyst　for　CO2RR.　©　2023