Presented is a novel application of pulsed field gradient (PFG)-NMR to the analysis of intercompartment exchange and the inner compartment droplet size distribution of a W/O/W multiple emulsion. The method involves monitoring the diffusional behavior of different components of the emulsion. Pfeuffer et al. [Pfeuffer, J.; Flogel, U.; Dreher, W.; Leibfritz, D. NMR Biomed. 1998, 11(1), 19-31.](1) and Price et al. [Price, W. S.; Barzykin, A. V.; Hayamizu, K.; Tachiya, M. Biophys. J. 1998, 74(5), 2259-2271.](2) proposed methods to extend Karger's PFG-NMR model of exchange between two compartments to accommodate spherical inner compartments. Each model enables the prediction of the oil membrane permeability, the inner compartment volume fraction, and a representation of the inner compartment droplet size distribution. The models were fitted to PFG-NMR experimental data of W/O/W emulsions. The Pfeuffer et al. model provided the best description of the observed experimental data. Predicted values of permeability and swelling were consistent with those reported in the literature for W/O/W emulsions. The addition of sorbitol to either the inner or outer water compartment resulted in an increase in the oil membrane permeability. Inner compartment droplet size distribution measurements indicate that swelling, rupture, and coalescence are likely to have occurred during the secondary emulsification and emulsion ripening. In its present form, the method still constitutes a fast, noninvasive (no addition of a tracer), and in situ method for comparative analysis of the permeability, stability, and yield of different formulations of multiple emulsions with a single PFG-NMR experiment.