The Ti-substituted heteropolytungstates K7[TiIVW11−BO40] and K6[VVTiIVW10PO40] have been synthesized and characterized by elemental analyses and spectroscopic techniques. Their redox properties have been studied by cyclic voltammetry, and the compounds were found to be more difficult to reduce than the unsubstituted heteropolyanion. The one- and two-electron reduced heteropoly blues of [VVTiIVW10PO40]6−, namely [VVTiIVW10PO40]7− and [VVTiIVW10PO40]8−, have also been prepared by chemical methods. Their optical spectra show low-energy intervalence charge-transfer bands as well as the expected d–d transitions. The optical and e.s.r. investigations indicate that VIV and TiIII are not vicinal in [VVTiIVW10PO40]8−.