A micropatterned multilayer film, which was fabricated from layer-by-layer electrostatic self-assembly of nitrodiazoresin (NDR)/poly(acrylic acid) (PAA) followed by photolithography, was utilized as a structured template for the biomimetic mineralization of calcium carbonate. Micropatterned CaCO3 films consisting of regularly aligned calcite crystals oriented in the <104> direction were selectively deposited on the patterned NDR/PAA multilayer film.