Compositional multiphase flow in subsurface porous media is becoming increasingly attractive due to issues related with enhanced oil recovery, CO2 sequestration and the urgent need for development in unconventional oil/gas reservoirs. One key effort to construct the mathematical model governing the compositional flow is to determine the phase compositions of the fluid mixture, and then calculate other related physical properties. In this paper, recent progress on phase equilibrium calculations in unconventional reservoirs has been reviewed and concluded with authors’ own analysis, especially focusing on the special mechanisms involved. Phase equilibrium calculation is the main approach to investigate phase behaviors, which could be conducted using different variable specifications, such as the NPT flash and NVT flash. Recently, diffuse interface models, which have been proved to possess a high consistency with thermodynamic laws, have been introduced in the phase equilibrium calculation, incorporating the realistic equation of state (EOS), e.g. Peng-Robinson EOS. In the NVT flash, the Helmholtz free energy is minimized instead of the Gibbs free energy used in NPT flash, and this thermodynamic state function is decomposed into two terms using the convex-concave splitting technique. A semi-implicit numerical scheme is applied to the dynamic model, which ensures the thermodynamic stability and then preserves the fast convergence property. A positive definite coefficient matrix is designed to meet the Onsager reciprocal principle so as to keep the entropy increasing property in the presence of capillary pressure, which is required by the second law of thermodynamics. The robustness of the proposed algorithm is demonstrated by using two numerical examples, one of which has up to seven components. In the complex fluid mixture, special phenomena could be captured from the global minimum of tangent plane distance functions and the phase envelope. It can be found that the boundary between the single-phase and vapor-liquid two phase regions shifts in the presence of capillary pressure, and then the area of each region changes accordingly. Furthermore, the effect of the nanopore size distribution on the phase behavior has been analyzed and a multi-scale scheme is presented based on literature reviews. Fluid properties including swelling factor, criticality, bubble point and volumetrics have been investigated thoroughly by comparing with the bulk fluid flow in a free channel.