We report on the development of conductive polymer-based cladding layers for use in multilayered electro-optic (EO) device structures. The waveguide claddings used in these studies were based on blends formed from the conductive polymer poly (ethylene dioxythiophene) with poly (vinylalcohol). Thin films of the blended materials were spun to form cladding layers having tunable conductivity and optical absorption. We tested these materials using a well-known guest–host core layer to determine their effect on the polar alignment of second order nonlinear optical chromophores. The claddings tested were shown to provide a large effective poling field across the active layer, and thus produced larger EO coefficients than systems having comparable, but more highly resistive, claddings.