Electrolytic reduction of carbon dioxide is a unique reaction which can produce many different major products such as formate (HCOO−) and formic acid (HCOOH). The interactions between CO2 electrolytes and the metallic electrodes lead to formation of various unstable intermediates which cause the reaction mechanism branch into different pathways. Previous literature suggest that bismuth could be the best suited for forming formate/formic acid, however there are many other metals known for the same reaction. The research in this thesis specifically aims to 1) establish effective detection methods for low formate concentrations (at the level of mM) in the highly concentrated electrolyte (2 MKHCO3) by high-performance liquid chromatography (HPLC), and 2) to conduct the comparative study on the metallic wire electrodes in reducing CO2 to formate in a flow cell electrolyzer, based on the established HPLC methods. Two HPLC methods were established with very high coefficient of determination (R2 > 0.99) for two different HPLC columns: reversephase and anion-exchange. The comparative study on metal wire electrodes showed significant formate production from bismuth electrodes, however, other metals such as Sn-Bi alloy, Au, and Ag consistently provided higher formate production rates.