Here,　the　molecule‐modified　Cu‐based　array　is　first　constructed　as　the　self‐supporting　tandem　catalyst　for　electrocatalytic　CO2　reduction　reaction　(CO2RR)　to　C2　products.　The　modification　of　cuprous　oxide　nanowire　array　on　copper　mesh　(Cu2O@CM)　with　cobalt(II)　tetraphenylporphyrin　(CoTPP)　molecules　is　achieved　via　a　simple　liquid　phase　method.　The　systematical　characterizations　confirm　that　the　formation　of　axial　coordinated　Co‐O‐Cu　bond　between　Cu2O　and　CoTPP　can　significantly　promote　the　dispersion　of　CoTPP　molecules　on　Cu2O　and　the　electrical　properties　of　CoTPP‐Cu2O@CM　heterojunction　array.　Consequently,　as　compared　to　Cu2O@CM　array,　the　optimized　CoTPP‐Cu2O@CM　sample　as　electrocatalyst　can　realize　the　2.08‐fold　C2　Faraday　efficiency　(73.2% vs　35.2%)　and　the　2.54‐fold　current　density　(‒52.9 vs　‒20.8 mA cm–2)　at　‒1.1 V　versus　RHE　in　an　H‐cell.　The　comprehensive　performance　is　superior　to　most　of　the　reported　Cu‐based　materials　in　the　H‐cell.　Further　study　reveals　that　the　CoTPP　adsorption　on　Cu2O　can　restrain　the　hydrogen　evolution　reaction,　improve　the　coverage　of　*CO　intermediate,　and　maintain　the　existence　of　Cu(I)　at　low　potential.