Stimuli-responsive polymer gels have recently attracted great attention due to their heat/solvent resistance, dimensional stability, and unique sensitivity to external stimuli. In this work, we synthesized thiol-functionalized TPE and constructed polymer gels through thiol-ene click reaction. The synthetic process of the polymer gels could be monitored by fluorescence emission of TPE moieties based on AIE mechanism. In addition, due to the dual redox- and acidresponsiveness of the polymer gels, in the presence of DTT and TFA, fluorescence quenching of the polymer gels can be observed. This stimuli-responsive characteristics endows the polymer gels with potential applications in fluorescent sensing and imaging, cancer diagnosis and selfhealing materials.