The conventional hydrometallurgical methods for recycling refinery spent hydroprocessing catalysts are ineffective in simultaneously removing all metals (Ni, V, and Mo) in a single-stage operation. In this study, a novel octadentate chelating agent, diethylenetriaminepentaacetic acid (DTPA-CHNO), has been proposed for the first time to remove toxic metals (Ni, V, and Mo) in a single stage of operation from an industrial spent atmospheric residue desulfurization (ARDS) catalysts. It was discovered that the efficient formation of metal-DTPA complexes was attained under the optimum experimental conditions (60 °C, stirring - 150 rpm, S/L ration (w/v) of 2.5%, 7.5% DTPA, and medium pH-9) that resulted in the high removal of Mo (83.6%), V (81.3%) and Ni (64.1%) from the spent ARDS catalyst. Kinetic studies suggest that the leaching process followed a semi-empirical Avrami equation (R > 0.92), which predicted that the diffusion control reaction controlled the leaching. Species distribution and ecological risk analysis of the remaining metals in the insoluble residue (mostly AlO) indicated that the potential bioavailability of the remaining metals (except Ni) was significantly decreased, and residue poses a low ecological and contamination risk (individual contamination factor <1). Furthermore, the textural properties of the residue (BET surface area-103 m/g and pore volume- 0.49 ml/g) were dramatically improved, suggesting that fresh hydroprocessing catalyst support can be synthesized using the leached residue. Compared to the conventional processes, the proposed chelating process is highly selective, closed-loop, and achieved high metal recovery in a single-stage operation while decreasing the environmental risks of the hazardous spent catalysts.