Herein, an electrocatalytic coupling system for selective ammonia and glycolic acid production over cathodic single‐atom Co (Co─N─C) and anodic PdNi alloying nanoparticles on the carbonized cellulose (PdNi/CBC), respectively are reported. As a cathodic electrocatalyst for nitrate reduction reaction (NtrRR), the Co─N─C displays remarkably high activity, delivering an NH3 yield rate of 20.5 ± 2.7 mg h−1 mgcat.−1 with a Faradaic efficiency (FE) of 95.5 ± 2.8% at −0.5 V (vs RHE). In situ spectroscopy combined with theoretical calculations unveiled the NtrRR mechanism on Co─N4 site. As an anodic electrocatalyst for ethylene glycol oxidation reaction (EGOR), the PdNi/CBC shows a high FE of 96.6 ± 1.7% for glycolic acid (GA) production at 1.6 V (vs RHE) and robust stability of 168 h. Remarkably, a proof of concept experiment of coupling electrocatalytic NtrRR with EGOR demonstrates that only an applied potential of −0.1 V (vs RHE) is required to reach a current density of 10 mA cm−2 for co‐producing ammonia and glycolic acid. As a result, the coupled NtrRR‐EGOR system can achieve an NH3 yield rate of 6.0 ± 0.6 mg h−1 mgcat.−1 and a GA yield rate of 16.8 ± 1.7 mg h−1 mgcat.−1 at −0.7 V (vs RHE).