The third-order nonlinear optical properties of a series of phthalocyanine–porphyrin complexes containing a sandwich-type bis(phthalocyaninato) europium(III) core and one or two zinc(II) porphyrin unit(s) were investigated by Z-scan techniques at 1064 nm. The second-order molecular hyperpolarizabilities of these complexes are in the order of 10−30 esu. The enhanced nonlinear properties are induced by the high delocalization of the electrons in the sandwich molecular structure, which may result in charge transfer between the central metal and the phthalocyanine ligands.Graphical abstractThird-order nonlinear optical properties of a series of phthalocyanine–porphyrin complexes containing a sandwich-type bis(phthalocyaninato) europium(III) core and one or two zinc(II) porphyrin unit(s) were investigated by Z-scan techniques at 1064 nm. The second-order molecular hyperpolarizabilities of these complexes are in the order of 10−30 esu.Highlights► Third-order nonlinear properties of porphyrin-bisphthalocyanines were investigated. ► Porphyrin-bisphthalocyanines are good materials with nonlinear optical properties. ► The enhanced nonlinearities are induced by high electron density and charge transfer.