Dielectric as well as electrical conductivity studies for polystyrene blended with polyaniline (PS/PANI) prepared by a casting method. These investigations indicated that PS/PANI 10% blend is found to possess the optimum electrical properties. For such reason, it was chosen to be blended with various contents of polyionic liquid (PIL) and carrying out further investigations in addition to the dielectric and electrical conductivity measurements. The mechanical, morphology, as well as thermal stability studies, indicates that PIL can act as a compatibilizer to PS/PANI blends. An increase in thermal stability as a result of the presence of PIL was detected by the thermogravimetric analysis. To increase the electrical conductivity of PS, two steps were done. The first step is blending PS with polyaniline (PANI). This step led to the conclusion that PS/PANI with concentration 10% PANI possess the optimum electrical properties as the values of sigma increase by increasing PANI content in the PS/PANI blends, but it is still in the range (10-10 S cm(-1)). This finding recommends such composites to be used for the anti-static applications. For higher performance, the second step was done by choosing such optimum PS/PANI blend to be blended with polyionic liquid. It is of great interest to find that the values of sigma (dc) increase two decants to be in the order of 10-8 S cm(-1) which are highly recommended to be used for electrostatic dissipation applications.