This study developed an effective and practical process for recovering vanadium as vanadium pentoxide (V₂O₅) from spent refinery catalysts. It involves four stages: leaching, purification, precipitation, and calcination. Vanadium was first leached using NaOH; then, the solution was purified by precipitation. Next, vanadium was recovered as ammonium polyvanadate, and finally, V₂O₅ was produced by calcination. The efficiency of the dissolution of vanadium reached 95% when the [NaOH] = 0.5 M, T = 25 °C, solid-to-liquid ratio = 1:10 g/mL, and time = 30 min. The pH of the leachate averaged ca. 10, but by decreasing it to 9, significant amounts of Al, Fe, and Si were removed from the solution. There was an estimated loss of 14% of vanadium during the precipitation of impurities, yet ca. 85% of it can be redissolved under the optimal leaching conditions. Finally, the purified leachate was subjected to the precipitation of vanadium by ammonium which was optimized using statistical software. The precipitation efficiency reached 76%; vanadium precipitated as ammonium polyvanadate. The resultant raffinate contained ca. 1.2 g/L of vanadium and was reconfigured for reuse within the process cycle. Next, the precipitate was calcined to produce V₂O₅ with a purity of over 99.5%. Experimental parameters were adjusted at each stage to optimize vanadium recovery while minimizing reagent consumption. By-products generated in each stage were reused in other processes, reducing waste production and vanadium loss. Finally, a life cycle assessment was conducted and revealed that the vanadium precipitation and calcination stages have the biggest impact on the environment in the developed process.