First to third-generation calix[4]resorcinarene core dendrimers, compounds 4a, 4b, 7a, 7b, 10a and 10b, were prepared via the divergent method in seven steps with the corresponding tetraphenyl- and tetra(hydroxyphenyl)calix[4]resorcinarenes(compounds 1a, 1b) as the starting material. The repeat units of the polyamidoamines of these dendrimers were obtained by the ammonolysis of ethyl calixarylacetates 2a and 2b with 1,3-diaminopropane, that is, amide derivatives with terminal amino groups, which in turn reacted with ethyl acrylate to give a higher generation of ester derivatives. The structures of these dendrimers were characterized by IR, 1H and 13C NMR spectrometries. The crystal structure of compound 2b with 12 ethoxycarbonylmethoxy groups was determined by X-ray analysis.