Azo dyes with electron-donating and neutral substituents in PMMA matrix and solution were prepared and characterized. High optical quality films were made for linear optical characterization of azo dyes. Two-photon absorption spectra, for investigated compounds dissolved in DMF, were obtained by Z-Scan measurements. The pi-pi* transition of investigated compounds is significantly red-shifted and overlaps with n-pi* transition. Accordingly azo dye with electron-donating group is more red-shifted compared to molecule with neutral group. Refractive index and efficiency of two-photon absorption cross-section for azo dye with neutral substituent is lower compared to azo dye with electron-donating substituent.