A multiresponsive switcher on both wettability and solid-state luminescence has great application potentials in novel smart devices. In this paper, a silole molecule of 1,2,3,4,5-hexaphenylsilole (HPS) was chosen to prepare thin films by spin-coating, and a solvent fuming dual-responsive switcher combining photoluminescent behavior and wettability was successfully achieved by changing the mode of solid-state molecular packing. This study suggests that HPS and other silole derivatives have a promising future for use in dual- and multifunctional switches in new technological applications.