Provided are a piezoluminescence structure, a piezoelectric structure, a manufacturing method thereof, and a high-sensitivity pressure sensor using the same. The piezoelectric structure includes: a plurality of perovskite material layers each including a material having an AnBnO3n perovskite structure; and interlayers inserted between the plurality of perovskite material layers and including A*O which is a metal oxide having reaction resistance to CO2. Here, A and A* are different elements and are one of an alkaline earth metal element, an alkali metal element, a lanthanide element, and a post-transition metal element, B is a transition metal element, O is an oxygen element, and n is a positive (+) integer. The piezoelectric structure may be a piezoluminescence structure.