Poly(3,4-ethylenedioxythiophene) (PEDOT) is an important material widely used in electronics for its hole conducting property. A novel strategy for the synthesis of nanoparticulate PEDOT was developed by emulsion droplet electrochemistry. Taking advantage of the space confinement in emulsions, PEDOT nanoparticles were size controllable without use of a separate template. Potential applications were investigated by implementing the PEDOT nanoparticle decorated electrodes as a supercapacitor and a hole transport layer in an organic light emitting diode.