Abstract The associative property of artificial neural networks (ANNs) and their inherent ability to “learn” and “recognize” highly non-linear and complex relationships finds them ideally suited to a wide range of applications in chemical engineering. Dynamic Modeling and Control of Chemical Process Systems and Fault Diagnosis are the two significant applications of ANNs that have been explored so far with success. This paper deals with the potential applications of ANNs in thermodynamics — particularly, the prediction/estimation of vapor–liquid equilibrium (VLE) data. The prediction of VLE data by conventional thermodynamic methods is tedious and requires determination of “constants” which is arbitrary in many ways. Also, the use of conventional thermodynamics for predicting VLE data for highly polar substances introduces a large number of inaccuracies. The possibility of applying ANNs for VLE data prediction/estimation has been explored using the back propagation algorithm. The methane–ethane and ammonia–water systems have been studied and the VLE predictions have been found to be accurate to within ±1%. Preliminary results confirm exciting possibilities of ANNs for applications to thermodynamics of mixtures. Advantages and limitations of this application are also discussed. An heuristic approach to reduce the trial and error process for selecting the “optimum” net architecture is discussed.