Breath figure imprinting, based on surface instabilities combined with fast polymer evaporation in a humid environment, enables the creation of micro-patterned membranes with tailored pore sizes. Despite being a simple procedure, it is still challenging to fully understand the dynamics behind the formation of hierarchical structuring. In this work, we used the breath figure technique to prepare porous PLA-based (polylactic acid) membranes with two distinctive additives, polyvinylidene fluoride (PVDF) and zinc oxide nanoparticles (ZnO NPs). The selection of these additives was governed by their unique properties and the potential synergistic effects; when blended with PLA, the addition of NPs leads to more uniform structures with tunable characteristics and potential multifunctionality. This article sheds light on the multifaced interactions that intricate the interplays between PLA, PVDF, and ZnO, thus governing their assembly. Through a comprehensive investigation, we scrutinize the impact of blending PVDF and different concentrations of ZnO NPs on the morphology and chemical properties of the final self-assembled PLA membranes while presenting an advanced understanding of the potential applications of PLA-self-assembly porous membranes in various industrial sectors.