Novel methods based on orienting and coating of ZnO nanoparticles were studied in order to obtain uniform, nano-sized and ultra-pure ZnO grains/particles after heat treatment. A 1 nm zinc-hydroxy-salt complex layer on the nanoparticle surfaces was revealed by thermogravimetry and infrared spectroscopy. This ‘phase’ gradually decomposed into ZnO during the heat treatment while sintering occurred above 600 °C, as revealed by scanning- and transmission-electron microscopy. The c-axis alignment of the nanoparticles provided smaller pores than those associated with non-oriented nanoparticles, presenting the means to obtain high-density ceramics. The orientation resulted in a smaller grain size after heat treatment than that of the nonaligned nanoparticles. Another method that involved three steps – silane coating, heat treatment and silica layer etching – was used to remove the ionic species from the nanoparticle surface while preserving its hydroxylated surface. These ultra-pure nanoparticles are expected to be key components in the development of HVDC insulation polyethylene nanocomposites.