The　utilization　of　Rh-based　catalysts　in　the　direct　production　of　ethanol　from　CO2　has　been　a　subject　of　significant　interest.　However,　to　date,　the　precise　active　sites　responsible　for　ethanol　generation　and　the　C-C　coupling　mechanism　remain　elusive.　In　this　study,　we　present　a　Rh-based　catalyst　featuring　nanoscale　Rh-Fe　alloy　sites,　which　achieved　an　ethanol　selectivity　of　49.1%　among　all　hydrocarbon　and　oxygenate　products　(CO　excluded)　under　relatively　mild　reaction　conditions　(3.0　MPa,　200　degrees　C,　with　a　low　metal　loading　of　＜=　1　wt　%).　The　formation　of　ethanol　proceeds　via　the　HCOO*　pathway　with　a　CO　insertion　mechanism　occurring　at　the　alloy　sites　with　a　specific　cluster　size,　where　CH2*　and　CO*　act　as　the　crucial　intermediates　for　C-C　coupling.　The　electron　interaction　within　the　Rh-Fe　alloy　sites　effectively　reduces　the　energy　barrier　for　the　formation　of　the　CH2CO*　intermediate,　thereby　facilitating　the　production　of　ethanol.　In　contrast　to　the　Rh-Fe　alloy　sites,　the　geminal-dicarbonyl　binding　configuration　of　CO*　intermediates　on　Rh　single　sites　favors　the　generation　of　byproducts　such　as　methane　and　methanol,　rather　than　ethanol.　This　research　offers　insights　into　the　active　sites　and　reaction　mechanism　of　hydrogenation　of　CO2　to　ethanol,　thus　enhancing　the　efficient　utilization　of　Rh-based　catalysts.