A facile synthesis of a series of polysiloxane-based ionic liquids (PNLs) is reported for the first time via straightforward thiol–ene reaction with high yield using three kinds of imidazolium ionic liquid monomers bearing a halide group and poly[(mercaptopropyl)methylsiloxane]. Unexpectedly, PNLs exhibit heterogeneous physical properties with the change of the modification molar ratio; meanwhile, their film-forming properties are well discussed. Furthermore, strong blue photoluminescence caused by the S→Si coordination bond and interesting self-assembly behavior in selected solvents were observed.