The calixarene crosslinked polysiloxanes were obtained by crosslinked (N-(β-aminoethyl)aminopropyl) modified silicon oil with 1,3-diglycidyl(calix[4]arene.)Their structures were characterized by infrared spectra and scanning electron microscopy.The thermal degradation behaviour of the calixarene crosslinked polysiloxanes with various content of calixarene under a nitrogen atmosphere was investigated by using thermogravimetry(TG),it showed that all the crosslinked polysiloxanes exhibited two-stage decomposition,the first decomposition peak was at about 391℃ and the second was at about 520℃,the ratio of the two fastest weight loss rates was varied with the content of calixarene.Under our experimental conditions,the calixarene crosslinked polysiloxane with 3% content of calixarene had the lowest rate of degradation during the first stage of decomposition.The thermal stability of calixarene crosslinked polysiloxanes was enhanced compared with that of (N-(β-aminoethyl)aminopropyl) modified silicon oil and 1,3-bis(2′,3′-epoxypropoxy)benzene crosslinked polysiloxane.