Production of valuable multicarbon (C3+) products through the electrochemical CO2 and CO reduction reactions (CO2RR and CORR) is desirable; however, mechanistic understanding that enables C-C coupling beyond the self-coupling of CO to valuable products is lacking. In this work, we elucidate the C-C coupling mechanism between CO and acetaldehyde, a reactive intermediate in both CO2RR and CORR, via combined isotopic labeling and in situ spectroscopic investigations. CO attacks the carbonyl carbon of acetaldehyde in the coupling, and the carbon in CO ends up in the hydroxymethyl group (-CH2OH) of the produced 1-propanol. While the coupling between CO and acetaldehyde does occur when the CORR is conducted with added acetaldehyde, only a minor fraction (up to 36%) of 1-propanol is from this pathway, and the majority of it is produced in the CORR by the self-coupling among CO. The adsorbed methylcarbonyl is proposed as the likely intermediate where the reaction pathway bifurcates to C-2 and C-3 products; i.e., it could either be hydrogenated to acetaldehyde and ethanol or couple with CO leading to the formation of 1-propanol.