We investigated linear optical and second-order nonlinear optical (NLO) properties of films of poly(bisphenol A carbonate) resin, and a newly synthesised titania/silica/hybrid sol-gel polymer resin doped with Disperse Red 1 (DR1) molecular chromophore. DC electric field induced second harmonic generation (SHG) technique has been used to monitor in situ the polar alignment and relaxation of orientation of the guest molecules in the corona-poled films. The temporal behaviour of the second harmonic signal was remarkably different in these two polymers both during poling and when the poling field was turned off. A fast decay of the second harmonic intensity was observed at room temperature in 3 wt% DR1-doped sol-gel film, and a long relaxation time constant was found in 13 wt% DR1-doped polycarbonate film. Resonantly enhanced d(eff) coefficient of about 9 pm/V was found in the sol-gel film, and 25 pm/V in the polycarbonate film at the fundamental wavelength 1053 nm. The d(33) values were about 20 pm/V, and 60 pm/V in these films, respectively. The SHG results were used to estimate the average rotation mobility parameter of DR1 molecules in the host polymers.