A bioinspired geometric templating of an electrospun PVDF substrate with hexagonal platelets of Mg-Al layered double hydroxide (LDH), an intrinsic anion conductor, is presented. The distinctive morphology restructures the internal pore geometry and modulates the dynamic wetting profile of PVDF, transforming it into a highly functional substrate for SAFC anion conducting membranes. The membrane fabricated with PVDF-LDH substrate exhibited exceptionally high durability (>140 degrees C), high anionic conductivity, ion exchange capacity (IEC), restricted swelling, and improved tensile strength, overcoming critical challenges associated with PVDF electrospun substrates and validating its immense potential as a high-temperature-stable and durable substrate for advanced fuel cell membrane applications.