Polymers made from ρ-dioxanone have been employed in the manufacture of absorbable surgical devices as biodegradable polymer. Purification of this ρ-dioxanone is an important step in order to high molecular weight poly(ρ-dioxanone). The separation and purification of ρ-dioxanone(PDX) from crude PDX has been studied by hybrid process. The hybrid processes were consisted of distillation(D), layer melt crystallization(LMC) and layer melt crystallization using solvent (SLMC). Especially, the highest purity PDX was obtained from the hybrid process arranged in the order of distillation - layer melt crystallization - layer melt crystallization using solvent.