A door to new opportunities: The stepwise hydrolysis of a diphosphorus trication is an efficient method for the preparation of an unusual ligand-stabilized dication that contains a novel cationic [P4O4]2+ framework (see Scheme; gray C, blue N, red O, orange P). This approach demonstrates the potential of the diphosphorus trication as a source for phosphorus building blocks to be used in the construction of novel cationic ring and cluster systems.