Photochemical and photoelectrochemical properties of ruthenium tris(2,2'-bipyridine) (Ru2+)-viologen (V2+) linked disulfides [RuCnVC(6)S](2) (n (number of methylene groups) = 3, 7) with different spacer-chain lengths and Ru2+ disulfides [RuCmS](2) (m = 13, 17) were compared. The luminescence intensity in CH3CN was in the order of [RuC13S](2) approximate to [RuC17S](2) > [RuC7VC6S](2) much greater than [RuC3VC6S](2) implying efficient photoinduced electron-transfer between Ru2+ and V2+ moieties in the linked compounds. The monolayer assembly of the compound was fabricated on a gold surface. In the presence of triethanolamine, the anodic photocurrent was clearly observed from the RuCnVC6S/Au (n = 3, 7) electrode (gold electrode modified with [RuCnVC(6)S](2)), and its intensity was substantially larger for n = 7 than for n = 3. Photocurrent action spectra for the RuCnVC6S/Au (n = 3, 7) electrodes were well correlated with the corresponding electronic absorption spectra in solution. The photocurrent from the RuC7VC6S/Au electrode was reduced more effectively by the coexistence of a water-soluble viologen as compared with the RuC3V6S/Au electrode. The photocurrent from the RuCmS/Au (m = 13, 17) electrode was very small. The results suggest that the spacer-chain length between the Ru2+ and the V2+ moieties profoundly affects the Ru2+-sensitized photocurrent.