Polymer/mosquito-repellent scaffolds exhibit increasing importance in long-lasting human skin protection to be used as wearable devices and allowing for controlled release of repellents. In this study, ethyl butylacetylaminopropionate (IR3535) was used as a human and environmental friendly active mosquito-repellent serving as a solvent to form functional poly(l-lactic acid) (PLLA) scaffolds by crystallization-based solid-liquid thermally induced phase separation. Crystallization of PLLA in the presence of IR3535 is faster than melt-crystallization of neat PLLA, and in the investigated concentration range from 5 to 50 mass % PLLA, its maximum crystallization rate increases with the PLLA content, by both, increases of the maximum crystal growth rate and of the nuclei density. By adjusting the polymer concentration and the crystallization temperature, microporous scaffolds of different fine structures are obtained, hosting the mosquito-repellent in intra- and interspherulitic pores for its intended later evaporation.