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TiO₂-II is a high pressure form of titania with a density about 2% larger than that of rutile. In contrast to the common polymorphs anatase, brookite and rutile its electronic structure and optical properties are poorly characterized. Here we report on a comparative electron-energy-loss-spectroscopy (EELS) study for which high resolution valence-loss and core-loss EELS data were acquired from nanocrystalline (<75 ​nm sized) titania particles with an energy resolution of about 0.2 ​eV. Electronic structure features revealed from titanium L_3,2 and oxygen K electron energy loss near-edge structures show a strong similarity of TiO₂-II with both rutile and brookite, which is attributed to similarities in the connectivity of octahedral TiO₆ units with neighboring ones. From combined valence-loss EELS and UV-VIS diffuse reflectance spectroscopy data the band gap of TiO₂-II was determined to be indirect and with a magnitude of ∼3.18 ​eV, which is very similar to anatase (indirect, ∼3.2 ​eV), and distinctly different from rutile (direct, ∼3.05 ​eV) and brookite (direct, ∼3.45 ​eV).