Poly(ethylcyanoacrylate) nanoparticles prepared by interfacial polymerisation on the basis of microemulsions were prepared in this study and both colloidal systems, nanoparticles and microemulsions, were analysed by visual observation and several microscopic techniques. Phase boundaries for the microemulsions of the two pseudoternary systems ethyloleate, polyoxyethylene 20 sorbitan mono-oleate/sorbitan monolaurate and water with and without butanol as a cosurfactant were determined by visual observation of the samples. Microemulsions containing liquid crystals were determined by polarisation light microscopy. Using freeze-fracture transmission electron microscopy and Cryo-field emission scanning electron microscopy the type of microemulsion (w/o droplet, bicontinuous, solution) was characterised. Nanoparticles prepared from the different types of microemulsion were additionally observed by conventional scanning electron microscopy. The size of the nanoparticles obtained from electron microscopy was in good agreement with particle sizing techniques (photon correlation spectroscopy) from earlier studies and no morphological differences could be observed in particles prepared from the different types of microemulsions. Cryo-field emission scanning electron microscopy proved to be a most valuable technique in the visualisation of the colloidal systems as samples could be observed close to their natural state.