A new group of bases with benzophenoneiminyl (bpi) moiety has been synthesized and characterized in this work. The title compound tris(benzophenoneimino)phosphane (P(bpi) 3 ) 1 was prepared with a convenient one-pot approach: benzophenone imine was deprotonated using MeMgCl and reacted with PBr 3 in diglyme. The method could be considered as a method of choice for preparing other (amino)phosphanes in case lithiointermediates and/or protonated phosphane is out of consideration. Phosphane 1 is further used to prepare a range of related phosphonium cations and phosphazenes. Phosphonium cations were deprotonated to assess the stability of the resulting phosphonium ylides. In some cases, the bulky substances were capable of forming PÀ N heterocycles. Experimental (MeCN) and computational (MeCN, THF, gas-phase) basicities of benzophenone imine, phosphane 1, phosphonium ylides, and phosphazenes, as well as some representative XRD structures, are presented and discussed.