A novel route for obtaining ordered microporous polylactide films has been explored using zinc oxide and a Schiff base. The SEM images reveal that the water vapor condensation near the surface of a polylactide solution containing a synthesized Schiff base and zinc oxide results in well-dispersed water droplets, which upon subsequent evaporation can assist breath figure patterning. The generation of ordered micropores at the film surface is attributed to the interaction between the surface +ve charge of well-dispersed zinc oxide particles and the delta-bearing water droplets from moisture. The potential for biocompatible applications has been revealed for the membranes by the cell viability assay against mice fibroblast (L929) cells and the hemocompatibility assay. The findings suggest an efficient route for the development of porous biodegradable polylactide membranes for various applications, typically for wound dressing.