AbstractA 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 PBr₃ in diglyme. The method could be considered as a method of choice for preparing other (amino)phosphanes in case lithio‐intermediates 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 P−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.