Fabrication and characterization of electro-optic modulators based on the novel organic electro-optic materials composed of self-assembled superlattices (SAS) were presented, both wet-dipping self-assembly and vapor phase deposition approaches were discussed. Prototype waveguide electro-optic modulators were fabricated using SAS films integrated with low-loss polymeric materials functioning as partial guiding and cladding layers.Promising electro-optic thin film materials including DTPT and PEPCOOH grown from the vapor phase were used for fabrication and test of electro-optic prototype modulators. Finally,the EO coefficient of tens of pm/V was obtained,which can sufficiently support high-speed and small size EO modulators.