We have developed a new grand canonical molecular dynamics (GCMD) algorithm to study microwave (MW) heating effects on competitive mixture sorption and have applied the method to methanol and benzene in silicalite zeolite. The new algorithm combines MW-driven molecular dynamics with grand canonical Monte Carlo (GCMC), the latter modeling adsorption/desorption processes. We established the validity of the new algorithm by benchmarking single-component isotherms for methanol and benzene in silicalite against those obtained from standard GCMC, as well as against experimental data. We simulated single-component and mixture adsorption isobars for conventional and MW-heated systems. In the case of the single-component isobars, we found that for dipolar methanol, both the MW and conventional heated isobars show similar desorption behavior, displaying comparable loadings as a function of molecular temperature. In contrast, nonpolar benzene showed no desorption upon exposure to MWs, even for relatively high field strengths. In the case of methanol/benzene mixtures, the fact that benzene is transparent to the MW field allows the selective desorption of methanol, giving rise to loading ratios not reachable through conventional heating.