We have demonstrated the successful preparation of polyvinyl alcohol (PVA) composed CuBi 2 S 3 polyionic (PI) composites. Polymer composites were sensitive to the external stimuli, the modified PVA moiety exhibits excellent electrical property as a function of temperature. The volume resistance measured by impedance analyzer (40 to 150 o C) under broadband frequency (50Hz -1MHz). The negative temperature coefficient (NTC) was observed in the temperature range of 40 to 150 o C. It offers the nonlinear resistivity, ρ = 10 5 (Ω-m) across pure PVA moiety. The influence of polycationic-ions crucial to obtain the gradual decrease of resistivity (ρ) up to 10 4 (Ω -m ). The thermistor characteristics were disclosed as function of polyionic loading (wt %).