A series of mixed-ligand 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen) rhenium(I) dicarbonyl complexes that are emissive in fluid solution has been prepared, which includes a new class of the type cis-[Re(CO)2(P-P)(N-N)]+ (where P-P is a chelating diphosphine and N-N is a chelating polypyridine ligand). The four synthetic routes that have been developed rely on either reactive triflate displacement or abstraction of labile chloro ligands, followed by the use of the strong trans-labilizing effect of P donors or direct use of the trans effect of P donors. The spectroscopic, photophysical, and electrochemical properties of these new complexes systematically vary with the net donor ability of the ligands in the coordination sphere, as shown by correlations with Lever's E(L) parameters. Lifetimes and quantum yields of the bipyridine complexes encompass a broad range, 25-1147 ns and ca. 0.002-0.11, respectively.