Electrochemical and photochemical reduction of CO2 are both well‐established, independent catalytic routes toward producing added‐value chemicals. The potential for any cross‐reactivity has, however, hardly been explored so far. In this report, we assess a system primarily using spectroelectrochemical monitoring, where photochemistry assists the cathodic activation of precursor complexes fac‐Mn(CO)3(2,2′‐bipyridine)Br and Mo(CO)4(6,6′‐dimethyl‐2,2′‐bipyridine) to lower the catalytic overpotential needed to trigger the electrocatalytic reduction of CO2 to CO. Following the complete initial 1e− reduction of the parent complexes, the key photochemical cleavage of the Mn−Mn and Mo−CO bonds in the reduction products, Mn(CO)3(2,2′‐bipyridine)2 and Mo(CO)4(6,6′‐dimethyl‐2,2′‐bipyridine).−, respectively, generates the 2e−‐reduced, 5‐coordinate catalysts, Mn(CO)3(2,2′‐bipyridine)− and Mo(CO)3(6,6′‐dimethyl‐2,2′‐bipyridine)2− appreciably closer to the initial cathodic wave R1. Experiments under CO2 confirm the activity of both electrocatalysts under the photoirradiation with 405 nm and 365 nm light, respectively. This remarkable achievement corresponds to a ca. 500 mV positive shift of the catalytic onset compared to the exclusive standard electrocatalytic activation. IR spectroelectrochemistry has unravelled the potential for photo‐assisted electrochemical reduction of Mn(CO)3(bipy)Br and Mo(CO)4(6,6′‐dmbipy) for triggering electrocatalytic reduction of CO2 at lower overpotentials. Utilizing the Mn−Mn and Mo−CO dissociative photochemistry of the 1e−‐reduced species, respectively, the active 5‐coordinate catalysts already operate near the parent cathodic waves, in a marked difference from the purely electrochemical routes.