An unconventional arsenic trioxide (As2O3) recovery process for unused injectable aqueous chemotherapeutic agents for leukemia treatment, having a concentration of 2 mg of As2O3/mL of H2O, was used as a case study by evaporative crystallization in a closed system under the pressures of 0.4, 0.7 and 1.0 atm. The yields for As2O3 solids recovered were 60 to 90 wt% with a purity in conformity with the As2O3 standard based on an HPLC assay. The recovered As2O3 solids were determined to be the arsenolite phase by PXRD with a particle size range of <10 μm.