Some examples of application of molecular dynamics simulations (MD) to the evaluation of dielectric properties of model compounds of polymeric chains are presented. Thus, a typical equilibrium property such as the mean squared dipole moment, 〈 μ 2〉, is calculated for 2-(acetyloxy) ethyl-2-(2-naphthyl)acetate (ANA), model compound of the side group of poly(2-{[2-(2-naphthyl)-acetyl]oxy}ethyl acrylate), and compared with experimental results. This calculation illustrates some of the difficulties of MD simulations since the 〈μ 2〉=5.8 D 2, obtained over a time span of 10 ns by employing the Tripos force field, is in agreement with the experimental result of 5.3 D 2, and yet, the analysis of probability distributions of the rotational angles of the molecule proves that it does not statistically sample the whole conformational space of the molecule within the rather long time allowed for the simulation. On the contrary, the Amber force field, with the same trajectory length of 10 ns, provides results that satisfies all conceivable tests. Dynamic properties such as life times of different conformations and dielectric relaxation times are also computed for 2-chlorocyclohexyl isobutyrate (CCHI), model compound of the repeating unit of poly(2-cyclohexyl acrylate) (PCCHA). Agreement between theoretical and experimental results is excellent.