In our experiment, aragonite crystals were prepared on nacre substrate with different treatment in a solution containing CaCl2 and sodium poly(4-styrenesulfonate) (PSS). It is shown that nacre substrates treated can induce the formation of aragonite crystals with different morphology and orientation corresponding to different treatment. We find that a uniform thin aragonite layer was formed on nacre substrate treated by sodium hypochloride (NaClO) solution after 30 min. The formation process is monitored and we suggest that amorphous calcium carbonate (ACC) in nacre plays a key role for this aragonite layer formation. Our work reveals a possible mechanism of the mollusk shell formation, which can be used to biomimetically synthesize functional biominerals. This work opens a new avenue for fabricating CaCO3-based hybrid materials with controlled structures, which shows the high performance and high function as well as the environmental benignity. (c) 2012 Elsevier B.V. All rights reserved.