Two triangular tri-nuclear, hetero-metallic copper(II)-nickel(II) complexes, [(CuL) 2 Ni{N(CN) 2 } 2 ]·H 2 O (1) and [(CuL) 2 Ni(NCS) 2 ]·H 2 O (2) have been synthesized by reacting “ligand complex” [CuL] with Ni(ClO 4 ) 2 in presence of polyatomic anions, dicyanamide (dca) or thiocyanate in methanol–water medium, where H 2 L is a N 2 O 2 donor di-Schiff base derived from 1,3-propanediamine and 2-hydroxyacetophenone. Both the complexes have been structurally and magnetically characterized. In both complexes, two [CuL] units coordinate to a nickel atom through the coordination of the phenoxido oxygen atoms forming triple phenoxido bridges between each Cu(II) and Ni(II). A couple of terminal dca or N-bonded thiocyanate ions complete the distorted octahedral geometry around Ni(II) in 1 and 2 respectively. Variable temperature magnetic susceptibility measurements show the presence of moderate antiferromagnetic exchange interactions mediated through the phenoxido bridges with J values (H=−J∑S i S i +1 ) of −49 and −42cm −1 for 1 and 2 respectively.