Molecular dynamics simulations and theoretical analysis were carried out to study the bulk and interfacial properties of carbon dioxide-methane-water and carbon dioxide-methane-brine systems under geological conditions. The density gradient theory with the bulk phase properties estimated using the cubic-plus-association (CPA) equation of state (EoS) can well describe the increase in the interfacial tension (IFT) of the CO2-water system in the presence of methane. The theoretical estimates of species mole fractions in the carbon dioxide-methane-water system are in good quantitative agreement with the experimental results. Furthermore, simulations of carbon dioxide-methane-brine system show that the IFT of the CaCl2 case is generally higher than that of the NaCl case. This is probably due to the stronger hydration of Ca2+ ions and their stronger repulsion from the interface as compared to Na+. While the overall shape of the ionic profiles is not much affected by the ion type, the water profiles show a local enrichment at the interface in the system with CaCl2. In contrast to the case of NaCl, the slopes of the plots of IFT vs CaCl2 concentration are dependent on temperature. Species mole fractions in the carbon dioxide-methane-brine system predicted by combining the CPA EoS with the Debye-Hückel electrostatic term are in good agreement with simulation results.