The lack of accurate knowledge for measuring monomer droplet size and droplet size distribution has hampered the further progress of miniemulsion polymerization. Monomer droplet size is probably the most important characteristics of a miniemulsion, influencing the miniemulsion stability and the nucleation mechanism. To date, several experimental techniques have been tested to measure miniemulsion droplet size, but none are convenient and accurate. This work presents a novel experimental technique, using a powerful new scanning transmission electron microscopy (STEM) imaging system, which allows transmission observations of wet samples in an environmental scanning electron microscopy (ESEM). This new imaging technique is a useful technique to directly measure droplet size and droplet size distribution.