In this study, we present self-supported vanadium-doped copper sulfide (Cu2S) electrodes as effective catalytic network for alkaline water electrolysis. The electrodes demonstrate a remarkably lower value of overpotential 375 mV for HER (hydrogen evolution reaction) and 403 mV for OER (oxygen evolution reaction) to generate 100 mA/cm2 current. A bi-functional electrolyzer incorporating these electrodes achieves a high current of 100 mA/cm2 at a cell voltage of 1.97 V. The positive influence of vanadium incorporation enhances the overall electrocatalytic activity of Cu2S and capable of generating the geometric current density of more than 500 mA/cm2 current for bi-functional electrolysis in industrial-scale alkaline electrolyte 5 M KOH at an elevated temperature of 60 °C, highlighting its potential for practical applications in renewable hydrogen production. Furthermore, the stability of electrodes was measured at different current densities at 20, 50 and 300 mA/cm2, suggesting the capabilities of electrodes for sustainable water electrolysis for green H2 and O2 production. DFT analyses confirms that the V-CusS exhibits superior performance owing to favourable H-adsorption energy on S-sites and minimum Gibb's free energy on V-sites. The study focuses on specific electrochemical performance metrics, offering insights into the promising utilization of vanadium-doped Cu2S electrodes for efficient water splitting in alkaline environments.