This study investigates phase equilibria and transport properties of five symmetric binary Lennard-Jones mixtures using molecular simulation and equation of state models. The mixtures are selected for their representation of different types of phase behavior and the research contributes to the development of simulation techniques, mixture theories and understanding of thermophysical mixture properties. A novel method is introduced for determining the critical end point (CEP) and critical azeotropic end point (CAEP) by molecular simulation. The van der Waals one-fluid theory is assessed for its performance in conjunction with Lennard-Jones equation of state models, while addressing different phase equilibrium types simultaneously. An empirical correlation is introduced to account for deviations between the equation of state and simulation that arise when using the same binary interaction parameter. This study also investigates the influence of the liquid–liquid critical point on thermophysical properties, which are found to exhibit no significant anomalies or singularities. System-size effects of diffusion coefficients are addressed by extrapolating simulation data to the thermodynamic limit and applying analytical finite-size corrections.