Electrochemical CO2 reduction reaction (CO2RR) has attracted a lot of interest as a highly potential CO2 utilization system. Due to the high overpotential in CO2RR, an effective catalyst is required. We report a metal organic hybrid catalyst (Co-PPy-C), which consists of Co and polypyrrole, as a highly active electrocatalyst for CO2RR. Co-PPy-C exhibited high Faradaic efficiency and metal mass activity for CO production at low over potential region. By density functional theory calculations, it was revealed that the catalytic site is the Co surface on which the deprotonated pyrrolic functionality in polypyrrole is adsorbed, and that the facile production of CO from CO2 is due to the CO adsorption on the Co being weakened by the charge transfer from the Co surface to the polypyrrole. This work reports a new and active non-noble metal catalyst for CO2RR, and provides the strategy of hybridization of metal and organic material to modify or enhance the catalytic activity of metal for CO2RR.