The electrochemistry and spectroelectrochemistry of Nb(V) in molten sodium chloroaluminate saturated with NaCl at 178-degrees-C were re-examined. It was determined that previous studies involved solutions of high oxide content. The reduction of NbCl5 in oxide-free melts was found to proceed via four steps at short times and low concentrations. At higher concentrations and long times, the reduction sequence was complicated by a chemical reaction which followed the initial reduction step. The effect of temperature on the electrochemistry of Nb(V) in sodium chloroaluminates and fluorochloroaluminates was examined; temperature had a marked effect on the behavior of Nb(V) in these melts, but no significant differences were observed between melts with and those without fluoride. Attempts to produce electrolytically niobium metal from Nb(V) in these melts met with limited success.