Electrostatic assembly is one of the bottom–up approaches used for multiscale composite fabrication. Since its discovery, this method has been actively used in molecular bioscience as well as materials design and fabrication for various applications. Despite the recent advances and controlled assembly reported using electrostatic interaction, the method still possesses vast potentials for various materials design and fabrication. This review article is a timely revisit of the electrostatic assembly method with a brief introduction of the method followed by surveys of recent advances and applications of the composites fabricated. Emphasis is also given to the significant potential of this method for advanced materials and composite fabrication in line with sustainable development goals. Prospective outlook and future developments for micro-/nanocomposite materials fabrication for emerging applications such as energy-related fields and additive manufacturing are also mentioned.