Glass is widely applied in fields of architecture, automobiles, optics and instruments due to its light transmission, wind resistance, sound and heat insulation. However, the light transmittance of traditional glass cannot change after the glass is formed, which limits the practicability of glass. In this study, an intelligent glass that can quickly and freely switch between transparency and opacity based on an optical‐thermal responsive hydrated poly(N‐isopropylacrylamide) film triggered by white light, infrared light, and direct thermal stimuli is developed. The fastest response time is ≈21 s under white light or 5 s by hand touch. A fatigue test of 250 cycles showed no obvious performance degradation. The transmittance of the intelligent glass changed reversibly between 88.5%–93.2% (transparent) and 25.5%–41.6% (opaque). The optical‐thermal response of the intelligent glass is attributed to the reversible phase transition of the hydrated poly(N‐isopropylacrylamide) film. This intelligent glass not only has obvious advantages in energy savings and emission reduction but also may be very useful for privacy protection, for example, in car windows, house windows, and office windows.