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 by approximately 119° and the Re‐L‐Re edges are twisted by approximately 88° from the idealized rectangular plane. The ReI metallacycle exhibits luminescence (λfluo. = 592 nm; λphos. = 731 nm) in CH2Cl2 at 77 K.