The experimental charge density of the Ni(II) complex of the Schiff base of (S)-N-(2-benzoylphenyl)-1-benzylprolinamide and glycine was derived from high-resolution single-crystal X-ray diffraction data (lambda = 0.5604 A) at low temperature (100 K) with synchrotron radiation at the beamline F1 using a CCD area detector. The central Ni atom is pseudo-square-planar coordinated by three N atoms [1.9414 (3), 1.8559 (3) and 1.8533 (3) A] and by one O atom [1.8620 (4) A]. The N(1) atom is 0.359 A above the plane defined by the atoms Ni(1), N(2) and N(3). The d-orbital population analysis reveals an oxidation state for the Ni atom of +2 with the configuration d(8) and a hole mainly in the d(x(2)-y(2)) orbital, located in the plane of the four ligating atoms. The prochiral reaction centre was examined by topological analysis.