The computational method described in this paper allows the calculation of the dielectric relaxation strength of an amorphous polymer based solely upon its chemical structure. The 4,4＇ oxydiphthalic anhydride (ODPA) dianhydride and bis-aminophenoxybenzene (APB) diamine based polyimides, (beta-CN) APB-ODPA and APB-ODPA were studied. Amorphous cells were constructed and then poled using molecular dynamics. Dielectric relaxation strengths of Delta epsilon = 17.8 for (P-CN) APB-ODPA and Delta epsilon = 7.7 for APB-ODPA were predicted. These values are in excellent agreement with the experimental values. It was found that both the pendant nitrile dipole and the backbone anhydride residue dipole make significant contributions to the polyimides＇ dielectric response. Specifically, it was shown that the difference in the magnitude of the dielectric relaxations is directly attributable to the nitrile dipole. The size of the relaxations indicate an absence of cooperative dipolar motions. The model was used to explain these results in terms of the average orientation of the nitrile and anhydride dipoles to within 51 degrees and 63 degrees, respectively, of the applied electric field.