The mechanical performance of a silica-based mineral nano-coating applied to alkali-resistant glass textile-reinforced composite materials aimed at structural strengthening is investigated experimentally. The silica nano-film is directly applied to the alkali-resistant glass fabric by sol–gel deposition. Two lime mortars are adopted as embedding matrix, which differ by the ultimate compressive strength and elongation. Uni-axial tensile tests of prismatic coupons are carried out according to the ICC AC434 guidelines. Remarkable strength and ductility enhancements could be observed in the silica-coated group, as compared to the uncoated group, for both mortar types. Digital image correlation, electron scanning and optical microscopy provide evidence of improved interphase strength. X-ray diffraction of the anhydrous mortars brings out the role of the mineralogical composition of the embedding media on the overall bonding properties of the composites. Consideration of design limits and energy dissipation capabilities reveals the crucial role of matrix ductility in bringing the contribution of interphase enhancement to full effect. We conclude that best performance requires optimizing the pairing between fabric-to-matrix adhesion and matrix ductility.