Knowledge of vapor-liquid equilibria is essential for chemical process design. Development of algebraically simple cubic equations of state, particularly Peng-Robinson and Soave-Redlich-Kwong equations of state has encouraged vapor-liquid equilibria calculation using the equation of state approach. To extend applicability to complex mixtures, several modifications to these equations of state were proposed. Also, many new mixing rules have been developed besides the already existing ones that incorporate excess free energy models. Some of these EoS/G(E) models are found to be applicable to complex systems in which the components can be highly polar, differ vastly in size or may be forming association. In spite of a large number of publications on this field, this subject is still open for further research. In this article, an overview on the work done using the most successful of the cubic equations of state, i.e., Peng-Robinson and Soave-Redlich-Kwong equations of state is presented. In the later part of this article, VLE predictions (using these two equations of state) of some interesting systems like water/hydrocarbon mixtures, polymer solutions, electrolyte solutions and refrigerant mixtures are discussed. The objective is to present the available information for ready reference that will prove to be useful from a designers point of view. It is seen from the existing literature that with a proper choice of equation of state and mixing rule based on the available knowledge on the properties of the system of interest, VLE of highly complex systems can be predicted with accuracy. Several comparative studies that are cited here (and discussed) will help the designer to pick-up the right combination for the system under investigation.