Eleven new complexes of the form cis-[Ru II (bpy) 2 (L A )] 4+ (bpy=2,2′-bipyridyl; L A =a pyridinium-substituted bpy derivative) have been prepared and isolated as their PF 6 − salts. Characterisation involved various techniques including 1 H NMR spectroscopy and MALDI mass spectrometry. The UV–Vis spectra show intense intraligand π→π ∗ absorptions and metal-to-ligand charge-transfer (MLCT) bands with two distinct maxima in the visible region. Small shifts in the MLCT bands correlate with the electron-withdrawing strength of the ligand L A . Cyclic voltammograms show quasi-reversible or reversible Ru III/II oxidation waves, and two or more ligand-based reductions with varying degrees of reversibility. The variations in the redox potentials correlate with changes in the structure of L A , and also with the MLCT energies. Differential pulse voltammetry allows the first reduction process for two of the complex salts to be resolved into two peaks. Single-crystal X-ray structures have been solved for three of the new complex salts and also for a pro-ligand salt. Two carboxylate-functionalised compounds have been tested as photosensitizers on TiO 2 -coated electrodes, but show only negligible efficiencies, in accord with expectations.