Plagioclase feldspars are among the most prevalent minerals in the solar system, and are present in many chondritic and achondritic meteorite families. Nevertheless, spectral features of plagioclases have never been unambiguously and directly observed in remote observations of asteroids. We report here the detection of an absorption band at 12.2 μm on Vesta spectra provided by ground-based spectral observations at the Subaru Telescope. This signature represents the first direct evidence of a widespread presence of crystalline Ca-rich plagioclase on Vesta and reveals that its regolith is comminuted to a very fine grain size, smaller than a few tens of microns, indicating that the mechanical brecciation process has been very effective. The crystalline nature of plagioclase strongly suggests that impacts alone cannot be the sole mechanism for regolith formation on Vesta and a milder process, such as thermal fatigue, should be invoked as an important and concomitant process Thermal fatigue should be considered a very effective process in regolith production and rejuvenation not only for near-Earth asteroids but even for large asteroids located in the main belt.