In this review, we describe recent progress on stimuli-responsive hybrid materials based on polyhedral oligomeric silsesquioxane (POSS) and their applications as a chemical sensor. In particular, we explain the unique functions originating from molecular assembly concerning POSS-containing soft materials mainly from our studies. POSS has an inorganic cubic core composed of silicon-oxygen (Si-O) bonds and organic substituents at each vertex. Owing to intrinsic properties of POSS, such as high thermal stability, rigidity, and low chemical reactivity, various robust hybrid materials have been developed. From the numerous numbers of POSS hybrids, we herein focus on the environment-sensitive optical materials in which molecular assembly of POSS itself and functional units connected to POSS should be a key factor for expressing material properties. We also explain the mechanisms of chemical sensors originating from these stimuli-responsive optical properties. Stimuli-responsive excimer emission and pollutant detectors, nanoplastic sensors with the water-dispersive POSS networks, trans fatty acid sensors, turn-on luminescent sensors for aerobic condition and fluoride anion sensors are described. We also mention the mechanochromic polyurethane hybrids and the thermally-durable mechanochromic luminescent materials. The roles of the unique optical properties from soft materials composed of rigid POSS, which doesn't have significant light-absorption and emission properties in the visible region, are surveyed.