An attempt has been made to prepare second-order nonlinear optic (NLO) materials based on cellulose diacetate and melamine derivatives. The NLO cationic chromophore, composed of 1,3-dimethyl-2-(4¢-N,N-dimethylaminophenyl)-azo-imidazole chloride and small amounts of 1,3-dimethyl-2-(4¢-N,N-dimethylaminophenyl)-azo-imidazole methylsulfate, was incorporated into a crosslink network formed from the reaction of cellulose diacetate with trimethylol melamine or hexamethylol melamine. The poled and cured NLO materials exhibited an electro-optic coefficient (r 13 ) of 1.03 or 1.42 pm/V, respectively, at the laser wavelength 1550 nm and a modulation frequency of 12.7 kHz; the r 13 values decreased to 97% or 86.6%, respectively, of the initial values after 4 days. The laser transmission loss was 0.58 or 0.6 dB, respectively. The crosslinked materials showed better temporal stability than the material of the host/ guest system with a doped cationic chromophore. The results of Fourier transform infrared spectroscopy, dielectric relaxation and thermogravimetry analyses proved the formation of a crosslink structure, and the degree of dielectric relaxation was shown to became higher if a crosslinker of too high functionality was used.