New neutral pentacoordinate nickel(II) complexes of the type [NiCl2(PR3)(P∩N)] [PR3 = PMe3, PMe2Ph, PMePh2; P∩N = 2‐(diphenylphosphanyl)aniline (P∩NH2), N‐methyl‐2‐(diphenylphosphanyl)aniline (P∩NHMe), N,N‐dimethyl‐2‐(diphenylphosphanyl)aniline (P∩NMe2)], as well as cationic tetracoordinate nickel(II) complexes of the type [NiCl(PR3)(P∩N)]+ have been synthesized and characterized both in the solid state and in solution. Interesting X‐ray structural data have been collected for each class of compounds, which show, inter alia, that the pentacoordinate neutral complexes can be isolated in two different molecular forms, namely square‐pyramidal or bipyramidal‐trigonal.