Laminated nanostructures in nacre have been adopted as models in the fabrication of strong, tough synthetic nanocomposites. However, the utilization of CaCO3 biominerals in these composites is limited by the complexity of the synthesis method for nanosized biominerals. In this study, we use the enzymatic reaction of urease to generate a nanoscale CaCO3 thin film to prepare CaCO3/polymer hybrid nanolaminates. Additional layers of CaCO3 thin film are consecutively grown over the base CaCO3 layer with the intercalation of organic layers. The morphology and crystallinity of the added CaCO3 layers depend strongly on the thickness of the organic layer coated on the underlying CaCO3 layer. When the organic layer is less than 20 nm thick, the amorphous CaCO3 layer is spontaneously transformed into crystalline calcite layer during the growth process. We also observe crystalline continuity between adjacent CaCO3 layers through interconnecting mineral bridges. The formation of these mineral bridges is crucial to the epitaxial growth of CaCO3 layers, similar to the formation of natural nacre. (C) 2016 Elsevier B.V. All rights reserved.