The optically tuneable nature of hybrid organic/inorganic heterostructures tailored by interfacing photochromic molecules with 2D semiconductors (2DSs) can be exploited to endow multi‐responsiveness to the exceptional physical properties of 2DSs. In this study, a spiropyran‐molybdenum disulfide (MoS2) light‐switchable bi‐functional field‐effect transistor is realized. The spiropyran‐merocyanine reversible photo‐isomerization has been employed to remotely control both the electron transport and wettability of the hybrid structure. This manipulation is instrumental for tuning the sensitivity in humidity sensing. The hybrid organic/inorganic heterostructure is subjected to humidity testing, demonstrating its ability to accurately monitor relative humidity (RH) across a range of 10%–75%. The electrical output shows good sensitivity of 1.0% · (%) RH−1. The light‐controlled modulation of the sensitivity in chemical sensors can significantly improve their selectivity, versatility, and overall performance in chemical sensing.