Mononuclear NiII complexes are particularly attractive in the area of single-molecule magnets as the axial zero-field splitting (D) for the NiII complexes is in the range of -200 to +200cm-1. Despite this advantage, very little is known on the origin of anisotropy across various coordination ligands, coordination numbers, and particularly what factors influence the D parameter in these complexes. To answer some of these questions, herein we have undertaken a detailed study of a series of mononuclear NiII complexes with ab initio calculations. Our results demonstrate that three prominent spin-conserved low-lying d-d transitions contribute significantly to the D value. Variation in the sign and the magnitude of D values are found to correlate to the specific structural distortions. Apart from the metal-ligand bond lengths, two different parameters, namely, Δα and Δβ, which are correlated to the cis angles present in the coordination environment, are found to significantly influence the axial D values. Developed magneto-structural D correlations suggest that the D values can be enhanced significantly by fine tuning the structural distortion in the coordination environment. Calculations performed on a series of NiII models with coordination numbers two to six unfold an interesting observation - the D parameter increases significantly upon a reduction in coordination number compared with a reference octahedral coordination. Besides, if high symmetry is maintained, even larger coordination numbers yield large D values. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.