The present work demonstrates the synthesis and characterization of adducts with bis(O,O 0 -diisopropylmonothiophosphato)nickel(II) complex, Ni{S(O)P(O i Pr) 2 } 2 -(L) n (n = 2, L = pyridine, 2-picoline, 3-picoline; n = 1, L = 2,2 0 -bipyridyl and 1,10-phenanthroline). The crystallographic investigation of Ni{S(O)P(O i Pr) 2 } 2 (C 5 H 5 N) 2 reveals distorted octahedral geometry around the central nickel(II) atom. The monothiophosphate moieties show anisobidentate coordination to the central metal, while the pyridine ligands are in cis positions. These nickel(II) adducts were characterized by elemental analysis, a range of spectroscopic techniques, and magnetic susceptibility measurement.