The synthesis and spectroscopic characterization of a new family of heteroleptic porphyrinate double-deckers are reported. The investigated compounds are represented by the formulae (LaH)-H-III(TPyP)(TPP) and [La-III(TMePyP)-(TPP)]I-3. UV-vis spectroscopy of the title complexes confirms the presence of a strong pi-pi interaction between the macrocycles in each derivative. With H-1 and 2-D NMR data, we were able to distinguish two major NMR regions: the endo, between the bonded macrocycles, and the exo, outside the macrocycles, which are characteristic features of porphyrinic double-deckers. Finally, the electrochemical study confirms the strong pi-pi interaction for (LaH)-H-III(TPyP)(TPP) and completes this first approach for the investigation of this new family of derivatives.