Understanding the thermodynamic behavior of charged and polar systems is essential for the design and development of many important chemical industrial processes, such as distillations, extractions, and catalysis. The importance of charged systems also extends to other fields, such as biological where almost all processes are based on electrolyte systems, as well as environmental, where depending upon the nature of the charge and polar system they can be either considered as contaminants (such as hydrogen sulphide) or as alternative solvents (such as ionic liquids) for a specific process. It is the industrial importance and well known non-ideal thermodynamic behavior of these systems that has lead to increasingly intense academic research and the development of predictive investigative tools. Traditionally, the description of thermodynamic behavior is obtained by macroscopic theories, which are based on phenomenological equations that contain adjustable parameters with a lack of physical meaning. In contrast, molecular-based equations of state, such as the statistical associating fluid theory (SAFT) are able to describe the thermodynamic behavior with adjustable parameters with physical meaning. In this sense, the SAFT approach can be considered as one of the most powerful equation of state for determining the thermodynamic behavior of complex systems. In a recent series of extensions to the SAFT-VR equation of state, McCabe et al. [Zhao, H. and McCabe, C. J. Chem. Phys 125 (2006), 104504; Zhao, H. and McCabe, C. J. Chem. Phys. In press (2007)] recently incorporated the different electrostatic interactions (ion-ion, ion-dipole and dipole-dipole) through modification of the reference fluid. Their expressions were obtained using the mean spherical approximation of Blum et al. [Blum, L. and Wei, D.Q. J. Chem. Phys. 87 (1987), 555; Wei, D. Q. and Blum, L. J. Chem. Phys 87 (1987), 2999] with the non-primitive model to account for the solvent molecules explicitly. Most of these studies were focused on describing the thermodynamic behavior of model pure and mixture systems and were compared with simulation data. In this work, we apply this extension to deal with real pure systems and mixtures of charged and/or polar fluids, such as aqueous solutions of electrolytes, ionic liquids, and hydrogen sulphide, amongst others. To do this, the intermolecular parameters for pure substances are obtained by adjusting the theory to the experimental values of the vapor pressure and saturated liquid densities. If needed unlike interaction parameters are adjusted in order to obtain a better description of the thermodynamic properties. The same parameters are used to predict the phase behavior at other thermodynamic conditions and the results compared with experimental data in order to demonstrate transferability and the predictive nature of the approach. KEYWORDS: SAFT, electrolytes systems, dipoles, phase behavior.