Langasite crystals (LGS) are known for their exceptional piezoelectric properties at high temperatures up to 1000 °C and more. In this respect, many studies have been conducted in order to achieve surface acoustic wave (SAW) sensors based on LGS crystals dedicated to high-temperature operations. Operating temperatures of more than 1000 °C and 600 °C for wired and wireless sensors, respectively, have been reached. These outstanding performances have been obtained under an air atmosphere since LGS crystals are not stable in high-temperature conditions under a low-oxygen atmosphere due to their oxide nature. However, if the stability of bulk LGS crystals under a high-temperature air atmosphere is well established, the surface deterioration under such conditions has been hardly investigated, as most of the papers dedicated to LGS-based SAW sensors are essentially focused on the development of thin film electrodes that are able to withstand very elevated temperatures to be combined with LGS crystals. Yet, any surface modification of the substrate can dramatically change the performance of SAW sensors. Consequently, the aim of this paper is to study the stability of the LGS surface under a high-temperature air environment. To do so, LGS substrates have been annealed in an air atmosphere at temperatures between 800 and 1200 °C and for durations between one week and one month. The morphology, microstructure, and chemical composition of the LGS surface was examined before and after annealing treatments by numerous and complementary methods, while the surface acoustic properties have been probed by SAW measurements. These investigations reveal that depending on both the temperature and the annealing duration, many defects with a corolla-like shape appear at the surface of LGS crystals in high-temperature prolonged exposure in an air atmosphere. These defects are related to the formation of a new phase, likely an oxiapatite ternary compound, the chemical formula of which is La14GaxSi9−xO39−x/2. These defects are located on the surface and penetrate into the depth of the sample by no more than 1–2 microns. However, SAW measurements show that the surface acoustic properties are modified by the high-temperature exposure at a larger deepness of at least several tens of microns. These perturbations of the LGS surface acoustic properties could induce, in the case of LGS-based SAW sensors operating in the 434 MHz ISM band, temperature measurement errors around 10 °C.