The controlled activation of white phosphorus, P-4, provides a key entry point I into many aspects of phosphorus chemistry. The activation and functionalization of P-4 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](2)(2+) obtained from the cyclo-1,3-diphospha-2,4-diazane [DippNPCl](2) for P-4 functionalization. This has enabled the targeted preparation of novel mono- and dicationic phosphorus-rich clusters [(DippNP)(2)(P-4)Cl](+) and [(DippNP)(2)(P-4)(2)](+). The utilization of such a bifunctional phosphenium Cation represents a rational and potentially versatile synthetic method for the assembly of large clusters using P-4 as a building block.