Four solvent-non-solvent pairs (ethylacetate-cyclohexane, dichloromethane-cyclohexane, acetone-cyclohexane and dichloromethane-n-hexane) with different solubility parameter differences were chosen to prepare ethylcellulose microcapsules containing theophylline by using non-solvent-addition phase separation method. The results showed that the surface morphology and release behaviour of microcapsules were greatly affected by different solvent-non-solvent pairs. The surface of the microcapsules prepared from the system of high solubility parameter difference was more smooth than those from the systems of low solubility parameter difference. The release rate of the drug from microcapsules decreased with increasing solubility parameter difference of the preparative system. The determination of the wall thickness and porosity of the microcapsules could reasonably explain the release characteristics. The porosity of the microcapsules decreased with the increase of solubility parameter difference of the preparative system, but the wall thickness of the microcapsules showed a corresponding increase. The release of the drug from various ethylcellulose microcapsules fitted first-order kinetics with biphasic release profiles.