A Volume-of-Fluid methodology for direct numerical simulation of interface dynamics and simultaneous interphase heat and mass transfer in systems with multiple chemical species is presented. This approach is broadly applicable to many industrially important applications, where coupled interphase heat and mass transfer occurs, including distillation. Volume-of-Fluid interface tracking allows investigation of systems with arbitrarily complex interface dynamics. Further, the present method incorporates the full interface species and energy jump conditions for vapour-liquid interphase heat and mass transfer, thus, making it applicable to systems with multiple phase changing species. The model was validated using the ethanol-water system for the cases of wetted-wall vapour-liquid contacting and vapour flow over a smooth, stationary liquid. Good agreement was observed between empirical correlations, experimental data and numerical predictions for vapour and liquid phase mass transfer coefficients. Direct numerical simulation of interphase heat and mass transfer offers the clear advantage of providing detailed information about local heat and mass transfer rates. This local information can be used to develop accurate heat and mass transfer models that may be integrated into large scale process simulation tools and used for equipment design and optimization. (C) 2010 Elsevier Ltd. All rights reserved.