The CaCO3/poly(ethylenimine) composite film was obtained in the presence of anionic poly(amidoamine) (PAMAM) dendrimer (G=3.5), whereas the formation of composite film was not observed without PAMAM dendrimer or with PAMAM dendrimer (G=1.5) judging from the results of scanning electron micrographs (SEM). The crystal phase of the CaCO3 film formed was found to be calcite by FT-IR and XRD analysis. The adsorption of PAMAM dendrimer on poly(ethylenimine) film might cause local high concentration of calcium ion and induce a formation of the CaCO3 film.