The global transition to a circular economyCircular economy and the risk of environmental pollution necessitates the sustainable recoveryRecovery of metal resources from different waste materials. In this work, we propose a hydrometallurgical recyclingRecycling of LiCoO2 cathode powder for the recoveryRecovery of two critical metals, cobalt and lithiumLithium. In particular, the selective dissolution of lithiumLithium has been explored for its simultaneous separation over cobalt which remained in the residual mass. In this context, the influential role of H2O2 and H3PO4 was investigated to obtain maximum dissolution efficiency of lithiumLithium, in contrast to a minimal leachingLeaching of cobalt in the solution. Over 99% separation of metals were achieved in leachingLeaching performed at the optimal condition of: H3PO4 = 1.0 M, H2O2 = 5 vol.%, temperature = 45 °C, agitation speed = 300 rpm, and time 90 min. This work provides critical insights into the selective leachingSelective leaching of LiCoO2 batteryBattery waste cathode materials.