Isothermal compression of poly (dimethylsiloxane), 1,4-poly(butadiene), and a model Estane (in both pure form and a nitroplasticized composition similar to PBX-9501 binder) at pressures up to 100 kbars has been studied using atomistic molecular dynamics (MD) simulations. Comparison of predicted compression, bulk modulus, and U(s)-u(p) behavior with experimental static and dynamic compression data available in the literature reveals good agreement between experiment and simulation, indicating that MD simulations utilizing simple quantum-chemistry-based potentials can be used to accurately predict the behavior of polymers at relatively high pressure. Despite their very different zero-pressure bulk moduli, the compression, modulus, and U(s)-u(p) behavior (including low-pressure curvature) for the three polymers could be reasonably described by the Tait equation of state (EOS) utilizing the universal C parameter. The Tait EOS was found to provide an excellent description of simulation PVT data when the C parameter was optimized for each polymer. The Tait EOS parameters, namely, the zero-pressure bulk modulus and the C parameter, were found to correlate well with free volume for these polymers as measured in simulations by a simple probe insertion algorithm. Of the polymers studied, PDMS was found to have the most free volume at low pressure, consistent with its lower ambient pressure bulk modulus and greater increase in modulus with increasing pressure (i.e., crush-up behavior).