Poly (caprolactone) (PCL) particles with the size distribution from 1 to 100 μm were prepared through solvent-induced phase separation, in which polyvinyl-alcohol (PVA) was used as the matrix-forming polymer to stabilize PCL particles. The cloud point data of PCL-acetone-water was determined by the titration method. PCL-acetone and PVA-water solutions, PCL-PVA gel, and PCL particles suspension were recorded by a digital camera. The morphology of PCL-PVA suspension and PCL particles were observed by optical microscopy and scanning electron microscopy, respectively. The size distribution of PCL particles was investigated by a particle size analyzer. Results from differential scanning calorimeter indicated that the main interaction between PCL and PVA were mediated through hydrogen bonding.