A synthetic route to 4-bromophenanthridine has been devised, enabling the construction of (4-diphenylphosphino)phenanthridine (1), a heterobifunctional Lewis base containing both phosphine and phenanthridine donors. The coordination chemistry of 1 with ions of late first-row transition metals nickel, copper and zinc has been explored, leading to the isolation and characterization of an organometallic Ni(II) complex, chloro(1-naphthyl)[(4-diphenylphosphino)phenanthridine]nickel (2), a halide-bridged copper(I) complex, bromo[(4-diphenylphosphino)phenanthridine]copper dimer (3), and a Zn(II) complex, bis(chloro)[(4-diphenylphosphino)phenanthridine]zinc (4). The solid-state structures of 2–4 demonstrate the ability of 1 to support both square planar and tetrahedral geometries. Electrochemical and luminescence studies revealed both metal and ligand-based redox activity and emissive properties.