The novel fluorinated polyimides with side-chain nonlinear optical (NLO) chromophores were synthesized from hydroxyl polyimides, followed by the Mitsunobu reaction with NLO chromophores. Molecular structural characterization for the resulting polymers was achieved by H-1 NMR, FT-IR, UV-Vis spectra, elemental analysis and gel permeation chromatography (GPC). The polymers exhibit excellent solubility in common organic solvents, good film-forming properties, high glass transition temperature (Tg) in the range from 193 to 200 degrees C and thermal stability up to 290 degrees C. The polyimides P1 and P2 containing hetarylazo chromophores with large hyperpolarizability possess a high electro-optic (EO) coefficient (r(33)), which is larger than that of the polyimide P3 attached DR1. Excellent temporal stability and low optical losses in the range of 1.9-2.1 dB/cm at 1.55 mu m were observed for these polymers. Such new NLO fluorinated polyimides are distinguished by an excellent combination of NLO activity, temporal stability, and optical loss. (C) 2009 Elsevier Ltd. All rights reserved.