Self-assembly of exfoliated monolayer titania sheets is investigated by detailed transmission electron microscopy and the force field calculations. It is demonstrated for the first time that slight but significant lattice distortions result in modified angular self-assembly of exfoliated monolayer Ti0.87O2 sheets. These findings significantly broaden current knowledge of the self-assembly of exfoliated nanoscale layered sheets, which may render the potential manipulation of self-assembly of nanosheets.