One-step surfactant-free, water-droplet templating has been developed as a fabrication method for a poly(lactide-co-glycolide) (PLGA) film that can be used as a model to investigate the relationship between solvent, monomer ratio, polymer concentration and humidity on its structure. The resulting material is a honeycomb-structured film. Formation of this structure was highly sensitive to solvent, monomer ratio, polymer concentration and humidity. Surfactant-free, water-droplet templating thus allows investigation of fabrication parameters and that PLGA monomer ratio selection is important for scaffold structure but not for MG63 cell attachment and proliferation.