The reactivity of diazadiphosphapentalene 1 towards various substrates was investigated. Reaction of 1 with ammonia–borane resulted in transfer hydrogenolysis concomitantly with the cleavage of a P−N bond. By treatment of 1 with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), oxidation took place at one of the phosphorus atoms of 1, and a PV/PIIImixed-valence derivative was isolated. At the same time, it was demonstrated that only one of the phosphorus atoms in 1 behaves as an electron donor for electrophiles and Lewis acids. The former afforded an intramolecularly coordinated phosphine-phosphenium species, whereas the latter demonstrates the ligand property of 1. UV irradiation induced rearrangement of 1 into another example of another diazadiphosphapentalene. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.