Since the initial report by Lehn et al. in 1979, ruthenium tris­(bipyridine) (Ru­(bpy)32+) and its numerous derivatives were applied as photosensitizers (PSs) in a large panel of photocatalytic conditions while the bis­(terpyridine) analogues were disregarded because of their low quantum yields and short excited-state lifetimes. In this study, we prepared a new terpyridine ligand, 4′-(4-bromophenyl)-4,4‴:4″,4‴′-dipyridinyl- 2,2′:6′,2″-terpyridine (Bipytpy) and used it to prepare the heteroleptic complex Ru­(Tolyltpy)­(Bipytpy)­(PF6)2 (1; Tolyltpy = 4′-tolyl-2,2′:6′,2′-terpyridine). Complex 1 exhibits enhanced photophysical properties with a higher quantum yield (7.4 × 10–4) and a longer excited-state lifetime (3.8 ns) compared to those of Ru­(Tolyltpy)2­(PF6)2 (3 × 10–5 and 0.74 ns, respectively). These enhanced photophysical characteristics and the potential for PS–catalyst interaction through the peripheral pyridines led us to apply the complex for visible-light-driven hydrogen evolution. The photocatalytic system based on 1 as the PS, triethanolamine as a sacrificial donor, and cobaloxime as a catalyst exhibits sustained activity over more than 10 days under blue-light irradiation (light-emitting diode centered at 450 nm). A maximum turnover number of 764 was obtained after 12 days.