The thermal quenching behaviors of the temperature sensitivity paints (TSP) composed of europium(III) thenoyltrifluoroacetonate (EuTTA) and Eu-phenanthrene complex (Eu-2) in polystyrene (PS), polymethylmethacrylate (PMMA) and epoxy resin (EP) were investigated. It is found that both the emission intensity and temperature sensitivity were not only affected by the luminescence probes, but also by the polymer matrix. The interaction between probes and matrix results in the alteration of both the non-radiation decay rate and the activation energy of the non-radiative process for the thermal quenching process,i.e., larger activation energy of the non-radiative process shows higher temperature sensitivity and less emission intensity. Therefore, it was confirmed that the temperature sensitivity and luminescent intensity of TSP depended not only on the luminescence probes but also on the polymer matrix.