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Polyfunctional aziridine/polyester microcapsules as control-release waterbe cross-linker were synthesized by multiple emulsion-solvent evaporation method. The results show that, a lower surface free energy with shell polyester is more favourable for the formation of microcapsules. Full encapsulating microcapsules are synthesized with the polyester with a surface free energy of 34.5 mJ/m2. Shell-to-core feeding mass ratio has a significant influence on the morphology and core content of the resulting microcapsules. Well defined spherical microcapsules with uniform shell thickness and core content at around 22% are produced at a shell-to-core mass ratio of 1:1. When 2.5% of colloid stabilizer is used, hollow spherical microcapsules are obtained. A high solvent evaporation rate results in wrinkling and porosity of the microcapsules, and an evaporation rate equivalent to solvent elimination in about 2 h provides a uniform rate of surface hardening. The characterization of the microcapsules by SEM and FTIR demonstrates that polyfunctional aziridine is encapsulated at the centre of the microcapsule. The microcapsules synthesized can be broken at a high shear rate.