In this study, a small amount of vinylphosphonic acid was used to produce fire-retardant copolymers and terpolymers from acrylonitrile and methyl acrylate. The structures of copolymer and terpolymers were elucidated by H-1-NMR and phosphorous analysis. Thermal decomposition of vinylphosphonic acid-containing copolymers and terpolymers started at lower temperatures than of poly(acrylonitrile-co-methyl acrylate). Methyl acrylate contributes to the thermal resistance of the terpolymers. Poly(acrylonitrile-co-methyl acrylate-co-vinylphosphonic acid) with a phosphorous content about 0.25% burned at a slower rate and emitted less smoke compared to poly(acrylonitrile-co-methyl acrylate). The burning tests showed that both copolymer and terpolymers containing vinylphosphonic acid behaved as a fire-retardant polymer. The phosphonate and phosphonic acid groups in the copolymer and terpolymers accelerate the cyclization of nitrile groups and inhibit the fire in the gas phase. Nanofibers were successfully produced by the electrospinning method from the copolymers and terpolymers containing vinylphosphonic acid moiety.