We report the first example of a Ni(II) complex that demonstrates sensitiser function in a Dye-Sensitised Solar Cell (DSSC). Complexes [Ni(dcbpy)(qdt)] (1), [Ni(decbpy)(qdt)] (2) and [Ni(decbpy)Cl-2] (3) (where dcbpy = 4,4'-dicarboxy-2,2'-bipyridine; decbpy = 4,4'-di(CO2Et)-2,2'-bipyridine; and qdt = quinoxaline-2,3-dithiolate) have been prepared. Characterisation was carried out using electrochemical, spectroscopic and computational techniques. Intensive visible transitions of l and 2 have been assigned predominantly to Ligand-to-Ligand Charge Transfer (LLCT) from the qdt to the diimine ligand, suggesting appropriate charge separation for application in a photoelectrochemical device. TiO2 sensitised with 2, following charge injection, processes a recombination time significantly long for photovoltaic function. In a DSSC, using I-/I-3(-) redox electrolyte, photocurrents and photovoltages of 0.293 mA and 521 mV were observed, with optimum values requiring TiCl4 post-treatment of TiO2 and co-adsorption of Chenodeoxycholic acid (Cheno). Although photovoltaic function was observed, the low photocurrent is attributed to a short-lived excited state lifetime resulting in poor charge injection from the Ni(II) sensitiser. (C) 2011 Elsevier Ltd. All rights reserved.