Bonding and redox properties of mono- and dititanium substituted 12-heteropolytungsto-phosphates and their complexes with bivalent Mn, Co, Ni and Cu are studied by UV-Vis, ESR and cyclicvoltammetric techniques. The heteropoly blue analogue [Ti^IIITi^IVW₁₀PO₄₀]⁸⁻ is unstable and its presence in solution is proved by optical and ESR spectroscopy. ESR results reveal that the odd electron is trapped on the titanium atom at 77 K. The optical electronegativity of Ti(III) in this heteropoly blue is estimated to be 2.4 from the intervalence charge transfer (IVCT) bands. X-ray powder diffraction results show that the complexes K₅M^II[Ti₂W₁₀PO₄₀].xH₂O(M^II = Cu or Mn) are isomorphous with K₇[Ti₂W₁₀PO₄₀].6H₂O. Electronic spectroscopy indicates very high symmetry around the bivalent metal ion M in the K₅M^II[Ti₂W₁₀PO₄₀].xH₂O complexes. This high symmetry is confirmed in K₅Cu[Ti₂W₁₀PO₄₀] by the observation of dynamic Jahn-Teller (JT) distortion at 300 K and static JT distortion at 77 K.