Emission, excitation spectra, quantum yields, and emission lifetimes are reported for the mixed ligand, bis-(2,2'-bipyridine)ruthenium(II) complexes cis-[Ru(bpy)2(L)(NO2)](+) with 4-substituted pyridines as ligands L [isonicotinamide (isnc), 4,4'-bipyridine (bipy), pyridine (py), 4-phenylpyridine (phpy), 1,2-bis(4-pyridyl)ethane (bpa), 4-picoline (mepy), 4-aminopyridine (apy), and 4-dimethylaminopyridine (ampy)] in EtOH-MeOH, 4:1 (V:V), at 77 K. Radiative, k(r), and nonradiative, k(nr), decay rate constants were determined for the series of complexes, and a linear dependence of ln k(nr) on E00, with E00 as the 0-0 energy gap determined by emission spectral fitting, was obtained with a slope of -(3.35 ± 0.23) × 10(-4) cm(-1). A linear correlation of E00 for cis-[Ru(bpy)2(L)(NO2)](+) complexes and Hammett substituent constant σ(p) is found.