The layer-by-layer assembly of layered double-hydroxide (LDH) nanocrystals was successfully accomplished by surface grafting using organic acids as coupling agents. The organic acids adsorbed on the crystalline sheet edges of LDH also play a key role in allowing or blocking the intercalation reaction of the multilayered LDH nanocrystals, thereby making it possible to form thin layers of organic-LDH nanocomposite architectures on solid substrates.