Sr2Ti7O14, a new phase, is synthesized by leveraging the innate chemical and thermodynamic instabilities in the SrTiO3-TiO2 system and non-equilibrium growth techniques. The chemical composition, epitaxial relationships, and orientation play roles in the formation of this novel layered phase, which, in turn, possesses unusual charge ordering, anti-ferromagnetic ordering, and low, glasslike thermal conductivity.