We numerically and theoretically study the stabilities of tilt thermal boundary layers immersed in stratified air. An interesting phenomenon is revealed: the stationary longitudinal-roll mode becomes unstable to some oscillating state even when the Grashof number is smaller than its corresponding critical value. By stability analysis, this phenomenon is explained in terms of a new three-dimensional wave mode. The effect of the tilt angle on the stability of the boundary flows is investigated. Since the new three-dimensional wave is found to be the most unstable mode when the title angle is between 30° and 64°, it is expected to play an important role in the transition to turbulence.