Biologically controlled mineralization features an orchestrated balance among various controlling factors such as spatial delineation, template promotion, crystal growth modification and cessation, and so on. Highly ordered calcium carbonate lamellae formed in the nacreous layers of mollusk (aragonite), the foliated calcitic layers of mollusk (calcite), or the semi-nacre of brachiopods (calcite) are excellent examples of the outcome of such synergistic control. Mimicking the concerted interplay of template promotion and growth inhibition as often utilized in biomineralization, we have synthesized macroscopic and continuous calcium carbonate thin films with thickness ranging from 0.4 to 0.6 mu m. The thin films were prepared at air/subphase interfaces by promoting mineral deposition with amphiphilic porphyrin templates, coupled with growth inhibition by the use of poly(acrylic acid) as a soluble inhibitor. Films formed at 22 degrees C were found to have a biphasic structure containing both amorphous and crystalline calcium carbonate. The crystalline regions were identified to be calcite oriented with the (00.1) face parallel to the porphyrin monolayer at the air/subphase interface. Films obtained in the early stage of formation at lower temperature (4 degrees C) displayed characteristics of a single amorphous phase. These observations suggest that films formed through a multistage assembly process, during which an initial amorphous deposition was followed by a phase transformation into the ultimate crystalline phase and the orientation of the crystalline phase was controlled by the porphyrin template during the phase transformation. The results provide new insights into the template-inhibitor-biomineral interaction and a new mechanism for synthesizing ceramic thin film under mild conditions.