The present study introduces a new route for the purification of cyclotrimethylenetrinitramine (RDX) explosive containing cyclotetramethylenetetranitramine (HMX) impurity, based on the digestion of crude materials in the binary solvent of acetone/water. Here, first, the solubility data, enthalpy of dissolution and mixing of RDX and HMX were determined experimentally in binary solvent. Then, the effects of various factors on the purification of RDX were studied statistically via response surface methodology (RSM) experimental design. In this technique, unlike the solubility data, unexpectedly HMX was dissolved with higher ratio and solid RDX was obtained with purity >99.5 wt.% and improved crystal morphology.