The use of a water-soluble octacationic bis-calix[4]arene with divergent cavities (BC(4)) as a templating agent for the assembly of a tetraanionic porphyrin (CuTPPS) has allowed the noncovalent synthesis of 2D or 3D multiporphyrin assemblies. Self-assembly of CuTPPS and BC(4) molecules proceeded under hierarchical control in a stepwise fashion to yield discrete and isolable supramolecular nanostructures containing up to 33 molecular elements (i.e., the CuTPPS/BC(4) 17:16 assembly, obtained in less than three hours). The formation of these species could be conveniently monitored by means of UV/Vis spectroscopy by following the absorbance of the Soret band at 412 nm. In particular, the attainment of the pivotal CuTPPS/BC(4) 5:4 species with a cruciform structure, as the key fork-point intermediate for the subsequent formation of the higher 2D and 3D assemblies, has been demonstrated by light-scattering studies and by an unequivocal synthesis of mixed-porphyrin/calixarene 5:4 species involving the use of two different types of metallated porphyrins, namely CuTPPS and MnTPPS. The remarkable stability of these assemblies permits a stepwise synthesis that makes it possible to choose the desired porphyrin sequence.