The controlled activation of white phosphorus, P4, provides a key entry point into many aspects of phosphorus chemistry. The activation and functionalization of P4 by N-heterocyclic carbenes and carbene-like main group element fragments is of considerable current interest. In this communication, we report on the first use of a disguised bifunctional Lewis acid [DippNP]22+ obtained from the cyclo-1,3-diphospha-2,4-diazane [DippNPCl]2 for P4 functionalization. This has enabled the targeted preparation of novel mono- and dicationic phosphorus-rich clusters [(DippNP)2(P4)Cl]+ and [(DippNP)2(P4)2]+. The utilization of such a bifunctional phosphenium cation represents a rational and potentially versatile synthetic method for the assembly of large clusters using P4 as a building block.