The biodegradable poly(ε-caprolactone)(PCL)/poly(ethylene imine)(PEI) microcapsules containing Al2O3 and fragrant oil were prepared with different PEI contents. The effects of stirring rate and concentration of the surfactant on the diameter and morphologies of microcapsules were investigated by using scanning electron microscope (SEM). Thermal behaviors were studied by using a differential scanning calorimetry(DSC), and the release behaviors of fragrant oil from microcapsule were characterized by UV/vis. spectrophotometer. As a result, the average particle size of the microcapsules decreased with increasing the stirring rate or concentration of the surfactant. The surface morphologies of the microcapsules were changed from smooth surfaces to skin-like rough surfaces as increasing the PEI content. These results were mainly due to the increased hydrophilic groups at the microcapsule surfaces, resulting in increasing the release rate of fragrant oil in the microcapsules studied.