A detailed picture of the local atomic environment of titanium in the novel titanosilicate ETS-10 has been derived from X-ray absorption spectroscopy aided by lattice energy minimization calculations. It is revealed that, in contrast to previous structural models for this disordered material, titanium exists in a distorted octahedral environment with long and short Ti-O bonds distributed within the chains of TiO6 octahedra. Plausible models for the extraframework cation distribution have also been proposed.