In this study, a series of tetraphenylethene (TPE) derivatives with 3-butenloxy moieties were synthesized. The developed TPE with different numbers of substituent groups showed controlled aggregation-induced emission performance and variable fluorescence properties, and theoretical calculations were carried out to explain these phenomena. TPE and its derivatives were further employed to construct composites through physical blending or a hydrosilylation reaction between the TPE derivative and polydimethylsiloxane. It was found that chemical bonding could improve the solubility of TPE derivatives in the polymer matrix without obvious phase separation. The fluorescence intensity of composites filled with TPE derivatives decreased with increasing temperature or mechanical force, thus giving the material a stimuli-responsive fluorescence property.