The triatomic compound titanium dioxide, TiO₂, was detected toward red hypergiant star VY Canis Majoris by Kamiński and co-workers, as reported in 2013. The detection was based upon initial observations made in 2010 with the Submillimeter Array located on Mauna Kea and then confirmed with the IRAM Plateau de Bure interferometer in 2012. Each facility consists of 6 radiotelescopes. Over two dozen lines from the two surveys were assigned to TiO₂. The detection in VY Canis Majoris was further confirmed with ALMA in two papers by De Beck and co-workers published in 2015 and 2016. De Beck also reported a tentative detection of TiO₂ toward the oxygen-rich, red giant Mira variable star R Doradus in 2018.

Titanium is in the first row of transition metals, also known as the d-block elements. Only a few other astromolecules are known that involve transition metals, including TiO, FeCN, and FeO.