This exertion introduces polyvinyl alcohol fiber/silica nanoparticles (poly vinyl alcohol (PVA)/SiO2 NPs) in the fly ash-based geopolymer at ambient curing temperature. The present study aims at investigating the structural properties (compressive, bond strength, fracture parameters (fracture toughness (KIc), crack mouth opening displacement (CMOD)), cyclic compression), durability (freeze-thaw), and fire resistivity of the newly developed PVA/SiO2 NPs mediated geopolymer. The outcomes suggest that geopolymers incorporated with 5% PVA fibers showed improved structural properties and durability as compared to other specimens. Investigation on the fire resistivity of the geopolymers exposed to different heating temperatures (400 °C, 600 °C, 800 °C), showed that geopolymers with PVA/SiO2 NPs significantly prevented the explosive concrete spalling. Microstructural studies confirmed that PVA fibers in the geopolymeric matrixes were well distributed and developed a fiber-bridging texture with improved performance. Addition of the nano-silica particles accelerated the heat evolution during the hydration process and the geopolymeric reaction (formation of sodium aluminosilicate N-A-S-H gel) at ambient curing environment.