Treatment of pink titanium(iii) triflate (0.045 M) with HF in triflic acid (CH3SO3H) converts Ti(iii) rapidly to a 1:1 mixture of TiIV and green TiII: (2 TiIII + 4 HF → TiF4 + TiII + 4 H+). This disproportionation is half complete when [HF] added is 0.027 M. Substituted 1,4-benzoquinones are reduced rapidly by Ti(iii) in the absence of fluoride, yielding straightforward logarithmic curves, but reactions of the same quinones with Ti(ii) in fluoride media exhibit more complex profiles, the major portions of which are zero order in oxidant. These reactions are strongly catalyzed by added Ti(iv). Analyses of complex curves are consistent with a reaction sequence initiated by Ti(ii)-Ti(iv) disproportionation, forming Ti(iii), which reacts with the quinone, yielding the quinhydrone, QH. The latter is rapidly reduced by Ti(ii). Values of rate constants obtained from these analyses are in agreement with those for reductions of quinones by Ti(iii), in the absence of fluoride. © The Royal Society of Chemistry 2010.