Abstract We report a straightforward strategy to design efficient N doped porous carbon (NPC) electrocatalyst that has a high concentration of easily accessible active sites for the CO 2 reduction reaction (CO 2 RR). The NPC with large amounts of active N (pyridinic and graphitic N) and highly porous structure is prepared by using an oxygen‐rich metal–organic framework (Zn‐MOF‐74) precursor. The amount of active N species can be tuned by optimizing the calcination temperature and time. Owing to the large pore sizes, the active sites are well exposed to electrolyte for CO 2 RR. The NPC exhibits superior CO 2 RR activity with a small onset potential of −0.35 V and a high faradaic efficiency (FE) of 98.4 % towards CO at −0.55 V vs. RHE, one of the highest values among NPC‐based CO 2 RR electrocatalysts. This work advances an effective and facile way towards highly active and cost‐effective alternatives to noble‐metal CO 2 RR electrocatalysts for practical applications.