Poly (vinyl alcohol) (PVA) – based solid electrolyte films with potassium thiocyanate (KSCN) were prepared by solution-cast technique. The pure and KSCN- doped PVA films have been investigated for the charge transport mechanism in the polymer electrolyte system by using the DC conductivity (The composition dependence and temperature dependence in 300-385K range) and transference number measurements. The graphs related to conductivity – temperature shows that an increase in conductivity with respect to rise in the temperature. At room temperature, the conductivity of the (PVA+KSCN) electrolyte is 10² times greater than that of pure PVA. The transference number data exhibit that the charge transport in this polymer electrolyte system is predominantly due to ions. The ionic transference numbers (t_ion)  lies in the range of 0.92 to 0.99 for the films of PVA with KSCN in the wt% ratios (90:10), (80:20) and (70:30).