Efficient all-optical poling of substituted norbornene ate-molecules-doped polymer thin films is presented. The growth and decay of photoinduced second-order susceptibility chi ((2)) has been studied. The possibility of encoding chi ((2)) at low seeding intensities (about 10 MW/cm(2) for fundamental and 100 W/cm(2) for second harmonic) is demonstrated. The value of encoded chi ((2)) in mono-norbornene-doped polymethylmethacrylate (PMMA) and poly-norbornene polymer have been found to be with the same order of magnitude despite the latter revealed considerably higher first hyperpolarizability. This is due to the rigidity of the poly-norbornene polymer backbone and the strong orientational correlation between pendant chromophores that reduce reorientation of molecules.