Gibbs ensemble Monte Carlo simulations Were Used to study the vapor-liquid equilibrium of binary mixtures of carbon dioxide + methane and carbon dioxide + difluromethane. The potential forcefields we employ are all atomistic models, and have not previously been mixed together to Study the vapor-liquid equilibrium of the binary mixtures. In addition, we characterize the microscopic Structure of these liquid Mixtures. In carbon dioxide + methane at 230 K and 56 bar, the microscopic structure of carbon dioxide in the mixture is the same as that in the Pure liquid. In carbon dioxide + difluoromethane at 283 K and 56 bar, the presence of carbon dioxide does not noticeably perturb the liquid structure of difluromethane, but (lie Structure of carbon dioxide is Subtly changed, due to a strong interaction between it and difluoromethane. The simulations in the isobaric-isothermal (NPT) ensemble agree well with the experimental data, except at the two extreme regions of the pressure range. The good agreement of most simulated state points with experimental data encourages one to develop more accurate potentials for predicting the thermodynamic properties Of these systems as well as other complicated Systems. which are less amenable to measurement by experiment.