The preparation of high-performance electro-optical materials is one of the key factors determining the application of optoelectronic communication technology such as 5G communication, radar detection, terahertz, and electro-optic modulators. Organic electro-optic materials have the advantage of a high electro-optic coefficient (~1000 pm/V) and could allow the utilization of photonic devices for the chip-scale integration of electronics and photonics, as compared to inorganic electro-optic materials. However, the application of organic nonlinear optical materials to commercial electro-optic modulators and other fields is also facing technical bottlenecks. Obtaining an organic electro-optic chromophore with a large electro-optic coefficient (r33 value), thermal stability, and long-term stability is still a difficulty in the industry. This brief review summarizes recent great progress and the strategies to obtain high-performance OEO materials with a high electro-optic coefficient and/or strong long-term stability. The configuration of D-π-A structure, the types of materials, and the effects of molecular engineering on the electro-optical coefficient and glass transition temperature of chromophores were summarized in detail. The difficulties and future development trends in the practical application of organic electro-optic materials was also discussed.