A poly(vinyl alcohol) (PVA)-based coating containing ammonium polyphosphate (APP) and sepiolite nanofillers (SP) and supported by a glass fabric was developed to fire-protect a glass-fiber-reinforced unsaturated-polyester-based (UP) polymer (GFRP). The fire behavior and thermal stability of the PVA coatings were characterized using thermogravimetric analysis (TGA) and a cone calorimeter. The coatings’ residues were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results from the cone calorimeter showed that the addition of sepiolite significantly improves the flame retardancy of PVA/APP/SP coatings. The addition of both additives promoted the formation of a cohesive layer composed of a silico-phosphate structure resulting from the reactivity between APP and SP. The fire resistance of the composite laminate protected by PVA coatings was evaluated using a cone calorimeter by measuring the temperature of the back face. Photogrammetry was used to assess the swelling of residues after heat exposure. The interaction between APP and SP in PVA coating leads to the formation of an effective thermal barrier layer. The presence of SP reduces the layer expansion but greatly decreases the backside temperature during the initial period of exposure. The effect was assigned to high thermal stability of the layer and its ability to dissipate heat by re-radiation.