Relaxation dynamics of poly(methyl methacrylate) (PMMA) and doped PMMA systems are investigated as a function of processing temperature and frequency. Polymer relaxations and changes in local mobility are responsible for chromophore reorientation and lead to a loss in second-order nonlinear optical (NLO) properties. Studying polymer relaxations enables the temporal and thermal stability of the NLO polymer systems to be more accurately and readily predicted. The polymer dynamics are studied by correlating mechanical and dielectric relaxations to polymer and chromophore relaxations that occur during chromophore reorientation in second harmonic generation experiments. Dielectric and mechanical relaxation techniques enable polymer relaxation dynamics to be observed over a broad frequency range. The plasticization effect of the NLO chromophores on the polymer relaxation dynamics is also investigated.