Titanium dioxide, TiO2, is a refractory species that could play a crucial role in the dust-condensation sequence around oxygen-rich evolved stars. We present and discuss the detections of 15 emission lines of TiO2 with ALMA in the complex environment of the red supergiant VY CMa. The observations reveal a highly clumpy, anisotropic outflow in which the TiO2 emission likely traces gas exposed to the stellar radiation field. We find evidence for a roughly east-west oriented, accelerating bipolar-like structure, of which the blue component runs into and breaks up around a solid continuum component. We see a distinct tail to the south-west for some transitions, consistent with features seen in the optical and near-infrared. We find that a significant fraction of TiO2 remains in the gas phase outside the dust-formation zone and suggest that this species might play only a minor role in the dust-condensation process around extreme oxygen-rich evolved stars like VY CMa.