A series of thermally stable organic/inorganic second-order nonlinear optical (NLO) composites via sequential self-repetitive reaction (SSRR) and sol-gel process has been developed. This SSRR is based on carbodiimide (CDI) chemistry. The difunctional azo chromophores (2,4-diamino-4'-(4-nitrophenyl-diazenyl)azobenzene (DNDA)) was reacted with excessive amount of 4, 4'-methylenediphenylisocyanate (MDI) to form poly-CDI, and subsequently trimellitic anhydride (TMA) was added to obtain poly(N-acylurea). The organic/inorganic composites containing prepolymer of phenyltriethoxysilane (PTEOS) and poly(N-acylurea) in different weight ratios (10:90, 30:70, 50:50, 70:30, 90:10 wt%) were prepared, respectively. The moderate glass transition temperature (T-g) characteristic of the poly(N-acylurea) allows the NLO-active polymer to achieve high poling efficiency. After in situ poling and curing process, the T(g)s of the composites were elevated, and higher than that of the pristine poly(amide-imide) sample. Electro-optical (EO) coefficients (r(33)) Of about 5.5 similar to 18.0 pm/V at 830 nm were obtained. Excellent temporal stability at 100 degrees C, and waveguide characteristics (3.1-4.2 dB/cm at 830 nm) were also obtained for these composites. Copyright (C) 2008 John Wiley & Sons, Ltd