In this work we investigated the second-order nonlinear optical properties of a group of Disperse-Red-1-based electro-optic fluorinated copolymers, synthesized with two fluorinated monomers: the hexafluoroisopropyl alphafluoroacrylate monomer and the alphafluoroacrylate monomer bearing the Disperse Red 1 chromophore. Copolymers, with a concentration of chromophore substituted groups ranging from 46% to 75% molar, were synthesized and deposited as single films on glass substrates, for second-harmonic generation, and as sandwich structures with electrodes, for nonlinear ellipsometry measurements. For large concentrations of substituted groups, cracking of the films was observed and did not allow for any electro-optic characterization by nonlinear ellipsometry. The second-harmonic generation tensor main component d 33 was retrieved by means of second-harmonic generation at = 1064 nm for each concentration. The results obtained for the copolymer with the lowest concentration are compared with those obtained by nonlinear ellipsometry at = 1550 nm and used as a calibration to infer information on the electro-optic properties at large concentrations. Stability of the poling-induced second-order nonlinear properties was checked by means of nonlinear ellipsometry. By using the temperature scanning technique, a depolarization temperature T dep = 124 ° C was measured, while the use of the isothermal relaxation technique allowed to observe two different decay regimes, a Vogel-Fulcher-Taman-Hesse one for temperatures above 110 ° C and an Arrhenius one for temperatures below 110 ° C, with activation energy E A 58 kcal/ mol. © 2005 American Institute of Physics.