Complex coacervation refers to the formation of distinct liquid phases that arise when polyelectrolytes are mixed under appropriate polymer and salt concentrations. Molecular-level studies of coacervation have been limited. In this work, a coarse-grained model of the polymers and the corresponding counterions is proposed and used to simulate coacervation as a function of polymer length and overall salt concentration. Several sampling methods are used to determine the phase behavior of the underlying polymers. In particular, the results of simulations in different ensembles are shown to be consistent and to reproduce a number of phenomena observed in experiments, including the disruption of complexation by increasing ionic strength or by decreasing molecular weight. The coacervate concentrations determined from phase behavior calculations are then used to examine the rheology of the corresponding materials. By relying on long dynamic simulations, we are able to generate the dynamic response of the material in the form of dynamic moduli as a function of frequency, which are also found to compare favorably with experimental measurements.