Spent sulfuric acid manufacturing (SAM) catalysts, rich in heavy metals, pose both environmental risks and resource potential. Safe disposal and efficient metal recovery are crucial for sustainability and waste valorization. This study developed and optimized a hydrometallurgical process for recovering vanadium (V(V)) from spent SAM catalysts through acid leaching and solvent extraction techniques. The spent catalysts were first homogenized into fine particles using a rod mill pulverizer for 20 min. Leaching with 5% v/v H₂SO₄ at room temperature and a solid-liquid ratio of 200 g/L dissolved 96.0% of V(V) within 10 min. Subsequently, 99.9% V(V) was extracted via liquid-liquid extraction using 50% v/v Aliquat 336 and 3% v/v iso-decanal diluted in D-80 diluent. The extraction was performed at pH 2 with an O/A ratio of 1 and a mixing time of 10 min. Stripping with NaOH yielded a pure V(V) solution, highlighting the process's efficiency. The V(V)-rich solution was then precipitated with NH4Cl at pH 7.5, forming vanadium salt, which was calcined at 400°C for 120 min to convert NH4VO3 into high-purity V2O5. This study demonstrates the effectiveness of combining leaching, solvent extraction, and precipitation for sustainable resource recovery from industrial waste.