We report herein a versatile strategy to fabricate ionomer-derived honeycomb-patterned films with favourable fluorescence, optical performance and hydrophobicity via a breath figure (BF) method. Taking well-defined poly(methyl methacrylate)–zinc acrylate (PMMA–Zn(AA)2) ionomer as the starting material, we have explored the influence of solvents and substrates on the morphologies of ionomer films obtained under 85% humidity. Fluorescent PMMA–ZnS hybrids were achieved subsequently in situ by exposing the ionomer solutions under H2S atmosphere. Due to the unique hierarchical hexagonal architectures, coupled with well-dispersed ZnS nanocrystals, the hybrid films obtained viaBF display fascinating fluorescence and vivid iridescent colours, with greatly enhanced hydrophobicity. Interestingly, these films contribute to ∼17.7% improvement of luminous efficacy for light-emitting diodes (LEDs) by virtue of their multifunctionality. This convenient and robust access to multifunctional honeycomb-patterned films by the BF method may find practical applications in extensive fields.
