Depends on the substances you got. If you have polystyrene sulfonate then it's probably conjugated with sodium cations to maintain its electroneutrality so it won't attract PEDOT electrostatically which in turn is probably in its neutral form. You can try however to dissolve them both at HCl, in order to subtract the sodium cation from PSS and to induce the existence of PEDOT+ by protonation. This may work well even though it depends also on the use you have for it.