Human tooth enamel has tightly packed c-axis-oriented hydroxyapatite (HAP: Ca10(PO4)6(OH)2) nanorods with high elastic modulus. Fabrication of an enamel architecture in vitro supports the repair of teeth using HAP; however, existing methods require complex and laborious steps to form an enamel-like structure. Here we present a very simple and effective technique for forming artificial enamel in near-physiological solution using a substrate composed of amorphous calcium phosphate (ACP) nanoparticles. Without any functionalized modification of the substrate surface, faint dissolution and successive phase transformation automatically induce formation of an intermediate layer of low-crystalline HAP nanoparticles, on which highly oriented HAP nanorods grow by geometrical selection. We also show that an enamel structure forms on a substrate of amorphous calcium carbonate when the surface nanoparticles react so as to form an intermediate layer similar to that in ACP. Our results demonstrate that there is a wide range of substrate choices for nanorod array formation. Contrary to current understanding, a stable surface designed in nanoscale is not essential for the growth of arranged guest crystals. Reactive amorphous nanoparticles and their transformation efficiently induce a nanorod array structure.