Unexpected high contrast mechanochromic, thermochromic and vaporchromic luminescence has been achieved through a simple introduction of an ester group to a pyrene skeleton and a series of stimuli-responsive materials based on pyrene-1-carboxylic esters were efficiently developed. The mechanistic investigation of stimuli-responsive luminescence indicates that the emission change might be ascribed to a reversible crystal-to-crystal transition. Furthermore, the electron-withdrawing effect of the ester groups to suppress the π–π interaction of the pyrene rings might be the key factor to trigger the promising stimuli-responsive luminescence.