Polysiloxane-modified tetraphenylethene (PTPESi) is successfully synthesized by attaching tetraphenylethene (TPE) units onto methylvinyldiethoxylsiloxane and subsequent polycondensation. Introducing polysiloxane into TPE has minimal effect on the photophysical properties and aggregation-induced emission behavior of TPE. The highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO) energy levels of PTPESi are located mainly on the tetraphenylethene moieties. The fluorescence intensity and the half width of the emission peak of PTPESi before and after annealing at 120 degrees C for 12 h are nearly the same, indicating high thermal stability and morphological stability. In addition, use of PTPESi film as a sensor toward the vapor-phase detection of explosives is also studied and it displays quite high fluorescence quenching efficiency and good reversibility.