We identified 122 unique metastable TiO₂ structures based on the final DFT calculations. Among these, 50 structures exhibit space groups that have not been observed in previously known TiO₂ polymorphs, as presented in Supplementary Figure . They differ in terms of local environment, connectivity and/or crystal symmetry. For instance, Structure IV, with space group R-3 in the trigonal system, features a unit cell comprising four octahedra and two square pyramidal units, showcasing a complex coordination environment distinct from typical TiO₂ polymorphs. Structure V, with the R3 space group, presents a rare arrangement of both tetrahedral and trigonal bipyramidal coordination polyhedra, highlighting the model's capability to predict uncommon structural motifs. Structure VI is an example of a configuration in the tetragonal system with space group P-4, formed through a unique three-dimensional arrangement of octahedra. It is impressive that the generative model can uncover plausible new structural configurations in a well-known binary space.