Navigating the Bio-Composite Landscape: A Strategic Reconstruction of Electrospun Starch–Zein Nanofibers

The transition from petrochemical plastics to sustainable biopolymers has created a critical demand for functional materials that do not compromise on performance. Starch and zein, due to their abundance and complementary nature, represent not just a chemical pair, but a techno-economic symbiosis: zein provides the hydrophobic shield, while starch offers the cost-effective structural volume. This review adopts a “Puzzle Theory” framework to synthesize over 80 peer-reviewed studies published between 2014 and 2025, categorizing the literature into established structural knowledge and unresolved functional limitations. Our analysis reveals that while fabrication protocols and molecular synergy are well-defined in approximately 65% of the surveyed literature, critical functional data remain largely absent. Specifically, fewer than 15% of studies investigate hydro-stability in high-humidity environments or bio-interface behavior, creating a disconnect between laboratory success and industrial application. We identify that current research disproportionately prioritizes dry-state morphology over wet-state mechanical integrity. To bridge the gap between academic prototypes and industrial reality, this article moves beyond general recommendations to propose concrete experimental benchmarks, including specific targets for wet mechanical integrity (>1 MPa), regulatory solvent compliance (<50 ppm), and scalable throughput. This article concludes by providing a strategic roadmap to bridge these gaps, arguing that future research must pivot from simple morphological characterization to developing “smart response” mechanisms and “green manufacturing” protocols to ensure commercial viability.