Polysulfone microcapsules containing vanillin were previously prepared by using a method based on phase inversion by immersion precipitation. Liquid water was used as the nonsolvent. Characteristics of that product were promising but further research was required. This work aims to prepare similar capsules by using vapor water as nonsolvent (vapor-induced phase inversion precipitation). The precipitation technique effect on capsules morphology and performance was studied. The products were morphologically characterized and significant differences were found only in the cross-section structure: if liquid water was used, macrovoids appeared in the wall; whereas by using water vapor, sponge-like structures were obtained. Finally, vanillin release was characterized, and release trends were the same for both preparations. Thus, the proposed process allowed the obtainment of capsules with similar performance. In addition, the use of water vapor showed a reduction of water consumption during the preparation.