The recovery of rare-earth elements and Fe from NdFeB waste has significant potential. However, conventional hydrometallurgical and pyrometallurgical processes are energy intensive, chemical consuming, and accompanied by waste emissions, resulting in low-value iron products. This study introduced a combined electrochemical–hydrometallurgical process for NdFeB waste recovery. Electrochemical analysis revealed the active dissolution of NdFeB waste under 370 mA/cm2, enabling Fe2+ reduction to Fe even in the presence of Nd3+. Electrolysis at 60 °C using Nd2(SO4)3 and FeSO4 as electrolytes, along with H3BO3 as a pH buffer, resulted in the uniform dissolution of waste, releasing Nd3+ and Fe2+ into the electrolyte, whereas Fe2+ underwent electrodeposition onto Fe at the cathode. Investigation of FeSO4 concentration revealed its influence on current efficiency, cathode-product properties, and energy consumption. When the concentration of FeSO4 was 0.5 M, a cathode product with 87.94 wt% Fe and 0.03 wt% Nd was obtained. Finally, Nd was recovered by hydrometallurgical high-temperature crystallization at 90 °C under N2 atmosphere, yielding Nd2(SO4)3·nH2O mixed crystals with 0.1 wt% Fe. The process formed a closed loop, consuming only FeSO4 and a minimal amount of H2SO4, with an energy consumption of 0.73–1.53 kW·h/kg NdFeB.