The relaxation spectra of polyacrylonitrile-poly(vinyl chloride) copolymer filament fibers were obtained by applying the experimental stress relaxation curves to the theoretical equation of relaxation spectrum. The theoretical equation of relaxation spectrum was derived from the Ree-Eyring and Maxwell model. The experimental of stress relaxation was carried out using a tensile tester with a solvent chamber. The determination of relaxation spectra was performed by computer calculation. From the relaxation spectra, the fine structures, viscoelastic properties and hole volumes of solid polymers were studied. It was observed that the relaxation spectra of these samples were directly related to the distribution of molecular weights and self diffusions of flow segments.