A new nonlinear optical (NLO) chromophore 4-dicyanomethylene-2-methyl-6- {4-[4-(N-ethyl-N-hydroxyethylamino)phenylazo]}styryl-4H-pyran (AZP), which features extended conjugated chain based on DCM laser dye, was synthesized and functionalized with alkoxysilane for materials processing. Hybrid films containing chromophore AZP and DCM were prepared via a sol-gel processing. The d(33) values of films containing AZP are 39-48 pm/V varying with concentration of chromophores, which is similar to that containing DCM. By tuning the organic content, the thermal stability of d(33) values can be significantly improved by about 30 degrees C, about 15 degrees C higher than those containing DCM. The residual rotational stress, along with cavity between chromophores and matrix, is proposed to contribute to the stability of NLO activity of hybrid films. (C) 2011 Elsevier B.V. All rights reserved.