This feature article has summarized our research on layer-by-layer deposition films of polymers on the basis of hydrogen bonding

coordination bonding and covalent bonding.Moreover

our discussion has focused on unconventional methods of layer-by-layer deposition that invovles supramolecular assembly in solution and layer-by-layer deposition at solid/liquid interface.It has been demonstrated how to combine structural architectures with functional assembly leading to controlling the physicochemical properties of the surfaces

including biomineralization

superhydrophobic coating

controlled assembly and release

and surface molecular imprinting.It is anticipated that this line of research is of significance for developing surface molecular engineering of polymer multilayer films.