Concentrated water in oil emulsions have been obtained with four different emulsifiers to study the effect of formulation parameters on the in vitro release of caffeine. The in vitro release was studied on polysulfone membranes. Among the four emulsifiers, only one gave a statistically higher release of caffeine after 15 h (at a fixed percentage of dispersed phase). The concentration of the emulsifier does not have a significant effect on the release of caffeine. In contrast, diffusion of caffeine from concentrated W/O emulsions has been found to be highly dependent on the internal phase volume. The flux of caffeine increases with the percentage internal water phase. The droplet diameter decreases and the apparent viscosity increases with the percentage of the dispersed phase. And, the shape of the droplets goes from spherical to polyhedral as the percentage dispersed phase is increased. However, the flux could be correlated neither with the apparent viscosity nor with the droplet diameter at a fixed percentage of the dispersed phase. Results suggest that the shape factor may have an influence on the release of caffeine from concentrated emulsions. All the release profiles followed a zero-order kinetic.