The bronze polymorph of titanium dioxide (TiO2-B) is interesting for many applications including high rate lithium ion batteries (LIBs), solar cells, photocatalysis, thermoelectrics and sensing, owing to its uniquely layered structure with open channels and highly asymmetric unit cell. However, such a metastable phase is extremely hard to obtain with high purity and crystallinity, significantly impeding its development in these fields. After more than 30 years since the first synthesis of TiO2-B in 1980, hydrothermal methods are still the dominant route to produce this material in powder form, with limited purity, randomized crystal orientation and unavoidable presence of lattice water. Here we report the discovery of a waterless process to synthesize hetero-epitaxial crystalline thin films of TiO2-B using pulsed laser deposition (PLD) onto its more stable variant, Ca:TiO2-B (CaTi5O11), which serves as a template. The growth mechanism and various microstructures in the thin films are clearly shown at the atomic scale. By aligning the more open channels to out-of-plane directions, extremely high rates of lithium ion transport, up to 600C, with extraordinary structural stability can be achieved. As the methods and equipment required are readily accessible to the extended research community, we anticipate our report may stimulate further studies on and applications of these materials, which are attractive in realms that extend beyond LIBs.