In this paper, an intumescent flame retardant treatment, obtained by a combination of vinylphosphonic acid (VPA) and methacrylamide (MAA), was applied to cotton fabrics. In order to improve the cross-linking degree onto cellulose polymers, potassium persulfate was used as initiator of a radical polymerization technique. The application on cotton was carried out by padding, followed by drying and a curing treatment. The treated samples were characterized by SEM, TGA and FTIR-ATR analyses and tested in terms of flammability and washing fastness. The thermal and fire behavior of the treated fabrics was thoroughly investigated. The results clearly showed that the VPA/MAA coating was able to exert a protective action, giving rise to the formation of a stable char on the surface of textile fibers upon heating, hence improving the flame retardant performance of cotton. Horizontal flame spread tests confirmed that the coated fabrics achieved self-extinction, and the residues well preserved the original weave structure and fiber morphology; at variance, the uncoated fabric left only ashes. A remarkable weight loss was observed only after the first washing cycle, then the samples did not show any significant weight loss, hence confirming the durability of the self-extinguishing treatment, even after five laundering cycles.