In this work, a facile approach to fabricating multifunctional smart windows by employing an ionic liquid-doped liquid crystal (LC)/polymer composite was reported. The composite was prepared via an established method of polymerization-induced phase separation while a commercial ionic liquid was doped into the composite as a supporting electrolyte. The smart window, which was prepared by sandwiching the as-prepared composite in two indium tin oxide (ITO) glasses, can exhibit a multifunctional mode. Specifically, the light transmittance and the coloration of the windows were regulated by different external stimuli. The electrically switchable transmittance of the window was achieved by an alternating current (AC) electric field and the window transformed into a transparent state from an opaque state under the AC field. The temperature was also used to realize the heat controllable transmittance, in which the window was turbid at a lower temperature and transparent at a high temperature. The electrically induced coloration of the window was manipulated by a direct current (DC) electric field and the window was changed into a green state from a colorless state under the DC field. This work is expected to open avenues to achieve a promising candidate for multifunctional smart windows with practical applications.