Electrical properties of PVC, PMMA and their 1 : 1 polyblends, before and after adding paranitroaniline into them, have been investigated as a function of temperature, electric field and dopant concentration, to study the mechanism of electrical conduction. The current was measured by applying d.c. voltage in the range 25-800 V at various thermostatically controlled temperatures (313-373 K). The results obtained predict the Schottky-Richardson conduction mechanism to be operative and d.c. conductivity of the blend lies intermediate between those of individual components. Further, the conductivity of the blend increases with temperature and applied electric field and also with the increase in concentration of dopant. To identify the mechanism governing the conduction, the activation energies in low temperature (LTR) and high temperature (HTR) regions have been calculated. The dielectric constant of the sample at various temperatures have been calculated which increased with increase in temperature. This is indicative of the diffusion of ions in space charge polarization at higher temperature. The study of XRD and FTIR supports the changes occurring in the conductivity of the blend.