The invention discloses a solid sample rapid thermal desorption mass spectrometry sampling device. The device conducts rapid thermal desorption on the solid sample by a thermal desorption chamber; and under the effect of pressure difference, thermal decomposition products enter into the mass spectrometry for analysis through an insulation transmission system. A high-temperature filter cloth is arranged at an outlet of the thermal desorption chamber and used to filter out particles with size larger than 50 mum, so as to ensure normal working of mass spectrometry. A quartz capillary and a three-way valve form a sample transmission system; the quartz capillary is used for transmission of the thermal desorption products; and the three-way valve is used to control starting and ending of sampling. The device provided by the invention can be combined with mass spectrometry to test thermal desorption products of the solid sample, and monitor the thermal desorption process of the solid sample, wherein no memory effect is generated in the process of analysis.