Spent hydrogenation catalysts are important secondary resources due to richness in the valuable metals of Ni, Mo and V. Recovery of valuable metals from spent catalysts has high economic value and environmental benefits since they are hazardous wastes as well. Traditional recycling processes including hydrometallurgical leaching and soda roasting-leaching have disadvantages such as generating large amounts of wastewater, long process, and low recovery efficiency of valuable metals. Thus, this paper proposed synergistic enrichment of Ni, Mo and V via pyrometallurgical reduction at 1400–1500 °C. The melting temperature and viscosity of slag were reduced through slag designing by software FactSage 7.1. The phase diagram of Al2O3-CaO-SiO2-Na2O-B2O3 was drawn, and low-temperature region (≤ 1300 °C) was selected as target slag composition. Ni, Mo, and V can be collaborative captured and recovered through the mutual solubility at molten state. Increasing the melting temperature and the amount of CaO, Na2O and C were conducive to improving the metals recovery rates. The kilogram-scale experiments were carried out, and the recovery efficiencies of Ni, Mo and V were 98.3%, 95.3% and 97.9% under optimized conditions: at 1500 °C, with the basicity of 1.0, 13.1 wt% SiO2, 7.0 wt% B2O3, 7.7 wt% Na2O and 20.0 wt% C. The distribution behavior of valuable metals was clarified by investigating the melting process of slag and the reduction in valuable metals. Ni was preferentially reduced and acted as a capturing agent, which captured other metals to form NiMoV alloys.Graphical abstract