Stimuli-responsive luminescent materials have received much attention as next-generation smart materials for various applications, including their use as biomedical probes, for the visualization of pollutants and sensing toxic gases. Boron-containing luminophores have been widely utilized to achieve such sensing materials because of their vacant 2p_z orbital, which is responsible for their Lewis acidity, electron-accepting properties, and ability to form complexes. In addition, polymeric structures often enhance stimuli-responsivity because slight environmental changes around the molecules can dramatically affect their molecular motions, shapes and physical properties. This review describes the development of stimuli-responsive materials using various kinds of luminescent boron compounds, focusing on the mechanisms of the sensing abilities and the molecular designs.