A family of di- and tetratopic redox-active ligands designed to generate discrete self-assembled metallacages is described, including UV/Vis spectrometry and cyclic voltammetry studies, X-ray diffraction on single crystals, and DFT calculations. A significant degree of conjugation between the π-donating bis(pyrrolo)tetrathiafulvalene (BPTTF) and the electron-withdrawing coordinating pyridyl units is observed. The tetrapyridyl ligand is able to self-assemble in the presence of cis-protected PtII complexes to produce the first examples of BPTTF-based cages endowed with a cavity prone to guest encapsulation. These metallacages undergo an original chemical conversion upon being heated in DMSO to afford Pt–dithiolene complexes, one of which was characterized by XRD. This reaction could be extended to alternative BPTTF derivatives.