Developing efficient catalysts for reducing carbon dioxide, a highly stable combustion waste product, is a relevant task to lower the atmospheric concentration of this greenhouse gas by upcycling. Selectivity towards CO-reduction products is highly desirable, although it can be challenging to achieve since the metal-hydrides formation is sometimes favored and leads to H evolution. In this work, we designed a cobalt-based catalyst, and we present herein its physicochemical properties. Moreover, we tailored a fully earth-abundant photocatalytic system to achieve specifically CO reduction, optimizing efficiency and selectivity. By changing the conditions, we enhanced the turnover number (TON) of CO production from only 0.5 to more than 60 and the selectivity from 6% to 97% after four hours of irradiation at 420 nm. Further efficiency enhancement was achieved by adding 1,1,1,3,3,3-hexafluoropropan-2-ol, producing CO with a TON up to 230, although at the expense of selectivity (54%).