Three dipyrromethane–diphosphine ligands containing phenyl (L1H2), ethyl (L2H2) and cyclohexyl (L3H2) groups at their meso positions and their nickel complexes were synthesized and structurally characterized. Treatment of Ph₂C(C₄H₃N)₂-1,9-(CH₂PPh₂)₂ (L1H2) with [NiCl₂(DME)] gave complex [NiCl₂(κ²-P,P-L1H2)] 2a. Conversely, the analogous reactions of L2H2 and L3H2 with [NiCl₂(DME)] showed a mixture of products containing both a pyrrolide nitrogen coordinated complex of type [Ni(κ⁴-P,N,N,P-L)] 3 without an exogenous base and a chelated complex of type 2a. In addition, all three ligands react with [NiCl₂(DME)] in the presence of a strong base to give a complex of type 3. Furthermore, a novel binuclear Ni(0) complex bearing L1H2 was characterized by X-ray crystallography. Both complexes 2a and 3 (0.5 mol% of loading) catalyze the transfer hydrogenation of a series of aromatic and aliphatic ketones (20 substrates) to their corresponding secondary alcohols using ⁱPrOH as a hydrogen source in the presence of KOH at 100 °C in 6 h. The kinetic trace of the catalytic reaction shows that the meso-phenyl substituted diphosphine coordinated nickel complexes perform better than the other two ligand coordinated nickel complexes.