We describe here the fabrication and characterization of novel organic electro-optic materials composed of self-assembled superlattices. The SAS structures are intrinsically acentric and exhibit large second harmonic generation and electro-optic responses. This approach using SAS electro-optic materials has advantages such as not requiring poling for creating nonlinearity in the films and efficient film growth on a variety of substrates over large areas. Prototype waveguide electro-optic modulators have been fabricated usgin SAS films integated with low-loss polymeric materials functioning as partial guiding and cladding layers. The waveguide EO modulators are fabricated using a multistep process including e-beam deposition, plasma-enhanced chemical vapor deposition, photolithography, and reactive ion etching. Electro-optic parameters such as the half-wave voltage and the effective electro-optic coefficient, and the velocity mismatch between the optical and radio frequency waves have been evaluated.