The electrostatic layer-by-layer technique for fabrication of multi-layered structures of various sizes and shapes using flat and colloidal templates coupled with polyelectrolyte layer-forming materials has attracted significant interest among both academic and industrial researchers due to its versatility and relative simplicity of the procedures involved in its execution. Fabrication of the multi-layered structures using the electrostatic layer-by-layer method involves several distinct stages each of which holds great importance when considering the production of a high-quality product. These stages include selection of materials (both template and a pair of construction polyelectrolytes), adsorption of the first polyelectrolyte layer onto the selected templates, formation of the second layer comprised of the oppositely charged polyelectrolyte and guided by the interactions between the two chosen polyelectrolytes, and multi-layering, where a selected number of layers are produced, and which is conditioned by both intrinsic properties of the involved construction materials and external fabrication conditions such as temperature, pH and ionic strength. The current review summarises the most important aspects of each stage mentioned above and gives examples of the materials suitable for utilization of the technique and describes the underlying physics involved.