Electro-optic (E-O) polymers have drawn great interest in recent years because of their potential applications in photonics devices such as high speed modulators and switches, optical data storage and information processing1–2. In order to have suitable materials for device fabrication, it is essential to design and develop polymeric material systems (active and passive polymers) with matched refractive indices, large E-O coefficients, good temporal and photochemical stability3–8 The E-O response of an active polymer commonly arises from the electric field induced alignment of its second-order nonlinear optical (NLO) chromophore, either doped as a guest/host system or covalently bonded as a side-chain. Because of the strong interaction among the electric dipoles, the poled structure is in a meta-stable state; the poled NLO chromophores which possess large dipole moment will tend to relax back to the randomly oriented state. As a result, the stability of the poled structure strongly depends on the rigidity of the overall material system. As it might be expected, the continuous increases of the rigidity and Tg of poled polymers imposes constraints on the selection of suitable chromophores that can survive the hightemperature poling and processing conditions. To circumvent this problem, we have developed a series of chromophores that possess conformation-locked geometry and perfluoro-dicyanovinylsubstituted electron-accepting group which demonstrate both good thermal stabilty and nonlinearity. This paper provides a brief review of these highly efficient and thermally stable chromophores and polymers for device applications.