Emulsions are ubiquitous in many consumer products, including food, cosmetics and pharmaceuticals. Whilst their macroscopic characterisation is well-established, understanding their microscopic behaviour is very challenging. In our previous work we investigated oil-in-water emulsions by studying the effect of water on structuring and dynamics of such systems. In the present work, we investigate the effect of surfactant concentration on microstructure and diffusion within the water-in-oil emulsion system by using low-field pulsed-field gradient (PFG) NMR studies carried out with a benchtop NMR instrument, in conjunction with optical imaging. The results reveal that at high surfactant concentration the formation of smaller droplets gives rise to a third component in the PFG NMR attenuation plot, which is mostly attributed to restricted diffusion near the droplet boundaries. In addition, structuring effects due to increase in surfactant concentration at the boundaries could also contribute to further slowing down water diffusion at the boundaries. As the surfactant concentration decreases, the average droplet size becomes larger and both restriction and structuring effects at the droplet boundaries become less significant, as suggested by the PFG NMR plot, whereby the presence of a third diffusion component becomes less pronounced.