The electrochemical conversion of carbon dioxide to valuable fuels is in the focus of academic and industrial research due to increasing demand for greener alternatives. Thus far, pyridine has been shown as the most promising homogenous electrocatalyst in the electrochemical reduction of CO₂ to methanol due to the low overpotential required to achieve faradaic yields of ca. 20%. Family of water-soluble vitamins B3 and B2 represent environmentally friendly class of electrocatalysts. Therefore, this study investigated the activity of nicotinic acid, nicotinamide and riboflavin to convert carbon dioxide to methanol (Figure). The optimization experiments revealed improvements in efficiency for methanol formation by varying the working electrode, electrocatalyst concentration, electrolysis duration and temperature. Vitamins B3 exhibit chemically reversible one electron reduction at ca. -0.5 to -0.6 V vs. Ag/AgCl with a Pt working electrode. The respective electrochemical systems are energy efficient with having overpotential less than 100 mV, however the evolution of hydrogen appears to be main competitive reaction on Pt. Riboflavin demonstrated chemically reversible reduction peak at ca. -0.65 V and -0.55 V vs. Ag/AgCl with Pt and GC electrode, respectively. Glassy carbon electrodes are known to have higher capacitance, resistance and relatively large overpotentials to hydrogen. Consequently, most methanol was generated on GC with 20 mM riboflavin and within the first 10 minutes of electrolysis, giving a yield of 19%. The result findings revealed that vitamins can served as the alternative electrocatalysts to a more expensive, toxic and less environmentally friendly pyridine. Recent developments and challenges in mechanism for future efficient and selective CO₂ reduction to methanol will be discussed in the frame of attractive and sustainable energy sources.