The thermodynamic parameters for the interaction of Cu2+, Ni2+, Co2+, Cd2+, and Ag+ with the new title ligand have been determined by titration calorimetry in 50% THF–methanol (V/V) at 25 °C. Ag+ exhibited remarkably higher complexation selectivity. Ag+ and several transition metal ions have been transported using this ligand as carrier in a bulk liquid membrane. Competitive Ag+–M2+ transport studies have also been carried out for the same system. In this membrane transport study, high transport of Ag+ was observed in both single and competitive Ag+–M2+ transport studies. The complex formation of N,N‘-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (P2N2) with silver, [Ag(P2N2)] (NO3), (1) is reported. Complex 1 has been characterized by X-ray crystallography. 1 is monoclinic, space group P21/n (No. 14), with cell dimensions a = 13.398(4) Å, b=12.577(5) Å, c = 21.521(4) Å, β = 100.14(2) Å, V = 3570(2) Å3 and Z = 4.