The coordination of a bis(dipyrrin) ligand (LH2) to Re(CO)5Cl delivers a dirhenium salt that serves as a precursor to a dinuclear phosphine compound or as a component of a metallacycle when combined with 4,4′-bipyridine (bpy) to furnish a tetranuclear [((CO)3Re)4L2(bpy)2] complex. The distorted nature of the metallacycle was determined by single-crystal X-ray diffraction revealing that the Re-bpy-Re edges are twisted ~119° and the Re-L-Re edges are twisted by ~88° from the idealized rectangular plane. The Re(I) metallacycle exhibits luminescence (λfluo. = 592 nm; λphos. = 731 nm) in CH2Cl2 at 77 K.