Electrostatic self-assembly was used to fabricate several samples of polymers known to have non-linear optical behavior. These samples characteristics were measured with interferometry and their electro-optic coefficients determined to be on the order that of LiNbO3. The self-assembled samples are shown to have an enhanced polar order compared to that of more traditional poled polymers. Furthermore, this polar order is intrinsic and thus doesn't require electric field poling and does not decay with time. The self-assembly process is therefore shown to possess great potential for the fabrication of high-speed electro-optic modulators for commercial and military applications.