K−Ta−Nb−O tetragonal tungsten bronze phase was grown on (11̅02) Al2O3 (R-plane sapphire) by pulsed laser deposition. The microstructure, structure, and chemical composition of the deposit were studied by scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectrometry, and transmission electron microscopy. The crystal structure was solved by precession electron diffraction as being tetragonal tungsten bronze-type structure with space group P4/mbm, refined cell parameters a = 12.537 ± 0.003 Å, c = 3.975 ± 0.001 Å, and composition K5.06(Ta0.57Nb0.43)10.99O30. The tetragonal potassium tantalum niobate growth follows two modes with respect to the substrate surface: (i) as single vertical right parallelepiped-shaped nanorods (50 to 100 nm wide and up to 1 μm in length) along the [001] direction and (ii) as in-plane attached crystals along the ⟨310⟩ direction. These two growth modes are understood as being governed by the plane termination of the substrate. This new phase is of potential interest due to the physical (dielectric, catalytic, etc.) properties evidenced for tetragonal tungsten bronze phases in numerous systems.