The miniaturization of chemical and biological processes in microfluidic devices and bioarrays is a major technological achievement. Microchips performing multiphase material synthesis operations could be a future step in this trend of miniaturizing technology. Here we show how electrically controlled chips can be used for the synthesis and manipulation of new types of particles with advanced structure. The method is based on a technique that allows freely suspended droplets and particles to be entrapped and transported using electric fields. The fields that hold and guide the droplets and particles are applied through arrays of electrodes submerged in the oil. Each of the microdroplets suspended on the surface of fluorinated liquid serves as a microscopic reactor, where the particles are formed by solidification of the carrier droplets. Controlled on-chip assembly, drying, encapsulation and polymerization were used to make anisotropic 'eyeball' and striped particles, polymer capsules and semiconducting microbeads.