We have shown that surface-enhanced Raman scattering (SERS) techniques may be successfully applied to the corona poling process of ultra-thin films to explain the poling behaviors of the side group non-linear optical (NLO) polymers. The poling kinetics for a flexible backbone based on poly(methyl methacrylate) (PMMA) was described by the usual bi-exponential function. However, the poling kinetics for a rigid backbone system, poly(p-phenyleneterephthalates) to which the NLO chromophores, N-(4-nitrophenyl)-(L)-prolinol(NPP) were attached through flexible spacers were governed by a single rate process. This observation is explained in terms of a strong coupling between the rigid backbone and its side groups.