An overarching challenge of the electrochemical carbon dioxide reduction reaction (eCO₂RR) is finding an earth-abundant, highly active catalyst that selectively produces hydrocarbons at relatively low overpotentials. Here, we report the eCO₂RR performance of two-dimensional transition metal carbide class of materials. Our results indicate a maximum methane (CH₄) current density of -421.63 mA/cm² and a CH₄ faradic efficiency of 82.7% ± 2% for di-tungsten carbide (W₂C) nanoflakes in a hybrid electrolyte of 3 M potassium hydroxide and 2 M choline-chloride. Powered by a triple junction photovoltaic cell, we demonstrate a flow electrolyzer that uses humidified CO₂ to produce CH₄ in a 700-h process under one sun illumination with a CO₂RR energy efficiency of about 62.3% and a solar-to-fuel efficiency of 20.7%. Density functional theory calculations reveal that dissociation of water, chemisorption of CO₂ and cleavage of the C-O bond-the most energy consuming elementary steps in other catalysts such as copper-become nearly spontaneous at the W₂C surface. This results in instantaneous formation of adsorbed CO-an important reaction intermediate-and an unlimited source of protons near the tungsten surface sites that are the main reasons for the observed superior activity, selectivity, and small potential.