We demonstrated the formation of single-crystal-like materials that contain preferentially orientedarrays of lead zirconate titanate (PZT) cube-shaped particles by self-assembly. Hydrothermally synthesizedPZT particles with a bulk composition of Zr/Ti = 70/30 were used in making microcrystal arrays. Spreadinga suspension containing PZT cube-shaped particles, 2-propanol, and mineral oil at the air−water interfaceproduced a one-dimensional planar array of PZT particles on the water surface. The array so formed wassubsequently transferred onto a flat or curved substrate. X-ray diffraction and electron backscattereddiffraction analyses revealed that most of the cube-shaped particles in the array were oriented with theirpseudocubic 〈001〉 direction aligned parallel to the normal direction of the substrate surface. Filling thearrays with matrixes produced monolayer or multilayer textured composites. The piezoelectric propertiesof oriented cube-shaped micron-sized particles in the self-assembled arrays were measured using a modifiedatomic force microscope to reveal the ferroelectric nature of the PZT arrays.