Conducting poly(o-toluidine) (POT) and poly(m-toluidine) (PMT) blends containing 10, 30, 50, 70, and 90 % wt/wt of polystyrene (PSt) were prepared by employing a two-step emulsion pathway. The bands characteristic of both polystyrene and POT/PMT are present in the IR spectra of POT-PSt and PMT-PSt blends. The UV-visible spectra of POT-PSt and PMT-PSt blends exhibit two bands around 313 and 610 nm, confirming that some amount of POT/PMT base is present in the blends. The EPR parameters such as line width and spin concentration reveal the presence of POT/PMT salt in the respective blends. The TGA, DTA, and DSC results suggest a higher thermal stability for the POT and PMT blends than that for the respective salts. The conductivity values of POT(70)-PSt(30) and POT(90)-PSt(10) blends are almost the same (1.1 Ο« 10 Οͺ2 and 1.3 Ο« 10 Οͺ2 S cm Οͺ1 , respectively) and these values are very close to that of pure POT salt, suggesting that POT can be blended with up to 30% wt/wt of PSt to improve its mechanical properties without a significant drop in its conductivity. The conductivity values of PMT-PSt blends are lower than those of the corresponding POT-PSt blends by two to three orders of magnitude, indicating that POT is a better system than PMT to prepare blends by this method. The dielectric constant and tan β¦ values of the blends increase with the amount POT/PMT and are greater than that of polystyrene.