A series of poly(vinylcarbazole)-based polymers containing sulfonyl-based nonlinear optical chromophores as the side chains were prepared conveniently through a postfunctionalization approach. In the polymers, the subtle structure of the chromophore moieties could be easily modified by the introduction of different isolation group, to adjust the property of the resultant polymers. The polymers exhibited good optical transparency, besides their good processability and thermal stability. The poled polymer films exhibited large second harmonic generation (SHG) coefficients of d(33) values (up to 28.6 pm/V) with excellent thermal stability (about 90% of the maximal SHG coefficients remain at similar to 110 degrees C). (C) 2008 Wiley Periodicals, Inc.