Although,　electrons　transfer　plays　an　important　role　in　achieving　the　electrocatalytic　CO2　reduction　reaction　(CO2RR),　it　is　scarce　to　regulate　the　electron　transfer　channels　for　enhancing　the　performance　of　CO2RR　via　rational　design.　Here,　based　on　different　solvothermal　conditions,　two　metal–organic　coordination　polymers　(MOCPs,　Ag-MOCP-1　and　Ag-MOCP-2)　electrocatalyst　for　CO2RR　were　obtained　by　the　same　Ag　ions　and　5-phenyltetrazolium　ligands.　Single　crystal　X-ray　diffraction　showed　Ag-MOCP-2　with　intra-&inter-layer　C–H···π　and　π···π　interactions,　while　Ag-MOCP-1　with　intra-layer　π···π　interactions.　The　intra-&inter-layer　π　interactions　in　Ag-MOCP-2　makes　it　show　multi-dimensional　electron　transfer　channels,　which　enable　Ag-MOCP-2　with　higher　electron　conductivities　and　lower　band　gap　than　Ag-MOCP-1.　And　the　Faradaic　efficiency　of　CO　for　Ag-MOCP-2　with　78.3　%　is　higher　than　that　for　Ag-MOCP-1　with　69.1　%　at　−1.08　V　vs　RHE,　and　the　maximum　difference　can　reach　22　%　at　−1.48　V　vs　RHE.　Based　on　the　same　central　metal　and　organic　ligands　of　the　two　MOCPs,　we　believe　that　multi-dimensional　electron　transfer　channels　make　a　predominant　contribution　for　improving　CO2RR　performance　in　this　work.　©　2022　Elsevier　B.V.