K–Ta–Nb–O tetragonal tungsten bronze phase was grown on (1102) 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 A, c = 3.975 ± 0.001 A, 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 in...