Titanium monoxide (TiO) was detected by Kamiński et al. in the circumstellar shell of the red hypergiant star VY Canis Majoris, as reported in 2013. The observations were made with a wide band survey with the 8 antenna Submillimeter Array on Mauna Kea and also with the 6 antenna IRAM Plateau de Bure interferometer in the French Alps. Ten transitions were identified. This was the first purely rotational detection of TiO, but TiO has been observed in visible star light via its electronic spectrum in stellar atmospheres since its discovery in Class M stars over a century ago, based upon pioneering spectroscopic studies by Fowler (1909) and others. TiO was first detected toward VY Canis Majoris by Wallerstein in observations reported in 1971.

Titanium monoxide is a simple diatomic molecule and quite different from the mineral with the same chemical formula. In fact titanium oxide (TiO) is not a naturally occurring mineral, though it can be made in the laboratory. The naturally occurring oxide of titanium is titanium dioxide (TiO₂), of which the mineral rutile is mostly composed.