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This review summarizes recent development of highly efficient organic electricoptic (OEO) materials and their applications in hybrid photonic devices. New generation of highly efficient EO polymers possessing large Pockels coefficients of 200-250 pm/V at 1.3 μm and excellent thermal and photochemical stability have been developed for advanced photonic devices. In addition, new pyroelectric poling process provides an efficient and reliable high field poling for EO polymers in multilayered thin films and nanophotonic waveguides. Using OEO materials as a key enabling element, significant progress has been made in the development of innovative hybrid EO devices, including EO polymer hybrid nanophotonic waveguides with high-index semiconductors, all polymer- and polymer/sol-gel-based EO modulators using low-refractive-index cladding layers, and EO polymer-based electric field sensors. At the end, this review also provides an outlook of future development of OEO materials and their hybrid systems for advanced photonic technologies.