The reaction between the coordinatively unsaturated phosphonodithioato complex [Ni(MeOpdt)2] (1) [MeOpdt = (MeO)(4-MeOC6H4)PS2−] and tptz [2,4,6-tris(2-pyridyl)-1,3,5-triazine] has been investigated. Spectrophotometric and conductometric titrations showed the formation of a neutral and an ionic species, i.e. [Ni(MeOdtp)2(tptz)] (2) and [Ni(tptz)2](MeOdtp)2 (3), in correspondence to 1 : 1 and 2 : 1 tptz : 1 ratios, respectively. XRD studies confirmed the formation of both complexes isolated in the compounds 2·MeOH and 3·4H2O. In the neutral complex 2 the central NiII ion features a distorted octahedral coordination, achieved through three N-atoms of tptz and three S-atoms belonging to two MeOpdt anions, one of which unexpectedly acts as a monodentate S-donor. In 3·4H2O, the two phosphonodithioato anions are non-coordinating and counterbalance the charge of the [Ni(tptz)2]2+ distorted octahedral complex. From the reaction of 2 with I2 and Br2, crystals of [Ni(tptz)2](I3)2 (5) and [Ni(tptz)Br(µ-Br)]2 (6) have been obtained. The dinuclear complex 6 features a structure showing tubular canals with openings of about 6 × 6 Å.