Fluorene-based polymer derivatives are promising materials for organic electronic devices because of their photoluminescence and electroluminescence, good film-forming ability, and favorable chemical and thermal properties. Although optical properties of polyfluorene have already been reported, most of the studies focused on the linear optical properties, whereas nonlinear optical characteristics have only recently received more detailed attention. Here, we report on two polyfluorene derivatives, poly(9,9-n-dihexyl-2,7-fluorenediyl) (LaPPS 10) and poly(9,9-n-dihexyl-2,7-fluorene-diyl-vinylene) (LaPPS 38), which present intense nonlinear absorption and fluorescence. Two-photon absorption cross-section properties of both polymers were characterized in the spectral range from 500 nm up to 900 nm, reaching peak values around 2000 Goppert Mayer units. Optical limiting behavior and two-photon-induced fluorescence of both polymers have also been investigated. Furthermore, the first molecular hyperpolarizability of the polymers was also studied using hyper-Rayleigh scattering. In addition, the three-photon absorption (3PA) spectra of both materials were also investigated, and 3PA cross-section values in the order of 1 x 10(-78) cm(6) s(2) photon(-2) were observed. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 747-754