To optimize the wetting performance of ionic liquids (ILs) on solid surfaces, which is important in catalysis, lubrication, and energy storage, it is critical to control the molecular arrangement of ILs at the IL/solid interface. Here, we report our experimental results, showing that tuning humidity is a facile and effective approach manipulating the molecular arrangement and thus controlling the macroscopic wettability of ILs on the mica surface. Fourier transform infrared spectroscopy, contact angle testing, and atomic force microscopy results showed that with the increase of humidity, more water adsorbs on the mica surface, which dissolves and mobilizes K+ on the mica. As a result, the cations of ILs occupy the empty spot left by the K+ and initiate the layering of ILs. The water-enabled ion exchange and IL layering processes result in not only the decrease of the IL contact angle on the mica but also the time-dependent contact angle. The finding here potentially provides a new dimension tailoring the performance of ILs at the IL/solid interface.