A microfluidic device has been used to create novel monodisperse polymeric oil-in-water emulsions of diameter 15–100 µm, stabilised by surfactants and polymers. The pulse field gradient nuclear magnetic resonance (PFG-NMR) signal attenuation function showed minima that allow a simple calculation of the droplet size and polydispersity. The presence of the minima is due to the restricted diffusion of molecules within the droplets, which can be analysed using standard solutions of the diffusion equation with a spherical boundary condition. However, even when a small population of polymer is unrestricted, the deep troughs in the attenuation function are obscured. The simultaneous water NMR attenuation function gives structural information about the continuous-phase matrix. The NMR size measurements were compared with those obtained by optical and confocal microscopy, and laser diffraction analysis.