Real-time monitoring of the corona-poling process that is used to create a bulk second-order nonlinear-optical susceptibility was accomplished by observing electrochromic shifts and intensity decreases of charge-transfer absorption bands in both dye-doped and covalently functionalized polymer films. By measuring small changes in the refractive-index anisotropy, the optical waveguiding technique was demonstrated to be a sensitive measure of the poling-induced order and its relaxation. The guest-host systems were formed from the dyes NN-dimethylaminonitrostilbene, NN-dimethylindoaniline (Phenol Blue), and 4-(N-(2-hydroxyethyl)- N-ethyl)-amino-4’-nitroazobenzene (Disperse Red 1), each dissolved in a poly(methyl methacrylate) matrix. The covalently functionalized polymers contained pendant para-nitroaniline (PNA) moieties. The first, poly(N-(4-nitrophenyl)allylamine), was formed from a poly(allylamine) derivative and is called PPNA. The second was based on poly(hydroxystyrene), with PNA attachment occurring between the phenol group and the PNA hydroxyethyl group; this polymer is named PHS-MENA. The final polymer is a linear epoxy (bisphenol A) with the PNA amino N atoms forming a link in the main chain; it is called Bis A-NA. A sample calculation demonstrated the use of experimental electrochromic spectral data to estimate the electro-optic coefficients. © 1990 Optical Society of America.