This study investigates the efficiency of electrochemical (electrolytic) processing for the selective recovery of tungsten and cobalt from WC–Co hardalloy scrap. A comprehensive literature review reveals that conventional pyrometallurgical routes suffer from high energy consumption, toxic gas emissions, and low selectivity, whereas electrochemical processing operates at low temperatures (20–30 °C), produces no harmful gases, and enables selective dissolution of cobalt while converting WC into tungsten oxide sludge. Experiments were performed using nitric acid (HNO3) and sulfuric acid (H2SO4) electrolytes under alternating current (AC) and direct current (DC). AC electrolysis produced no measurable tungsten sludge due to alternating redox cycling, whereas DC electrolysis resulted in intensive anodic dissolution of WC and the formation of tungsten oxide sludge with simultaneous cobalt dissolution. Optimal results for VK6, VK8, and VK15 alloys were achieved at 14.25% HNO3and 16.33% H2SO4, respectively. Addition of (NH4)2SO4 significantly enhanced sludge formation, while electrode spacing and cathode surface area strongly affected reaction kinetics. SEM and EDXRF analyses confirmed that the obtained product consisted of tungsten oxides. The findings provide a scientific basis for designing industrial-scale, energy-efficient, and environmentally safe electrochemical recycling technologies for WC–Co waste.