Conventional water electrolysis relies on expensive membrane-electrode assemblies and sluggish oxygen evolution reaction (OER) at the anode. Here, we develop an innovative and efficient membrane-free water electrolysis system to overcome these two obstacles simultaneously. This system utilizes the thermodynamically more favorable urea oxidation reaction (UOR) to generate clean N2 over a new class of Cu-based catalyst (CuXO), fundamentally eliminating the explosion risk of H2 and O2 mixing while removing the need for membranes. Notably, this membrane-free electrolysis system exhibits the highest H2 Faradaic efficiency among reported membrane-free electrolysis work. In situ spectroscopic studies reveal that the new N2Hy intermediate-mediated UOR mechanism on the CuXO catalyst ensures its unique N2 selectivity and OER inertness. More importantly, an industrial-type membrane-free water electrolyser (MFE) based on this system successfully reduces electricity consumption to only 3.87 kWh Nm-3, significantly lower than the 5.17 kWh Nm-3 of commercial alkaline water electrolyzers (AWE). Comprehensive techno-economic analysis (TEA) suggests that the membrane-free design and reduced electricity input of the MFE plants reduce the green H2 production cost to US$1.81 kg-1, which is lower than those of grey H2 while meeting the technical target (US$2.00-2.50 kg-1) set by European Commission and United States Department of Energy.