A facile sensor system based on heat-treatment solid phase microextraction and Surface-Enhanced Raman Scattering (HT-SPME-SERS) was established for in-situ detection of isocarbophos in complex tea matrix. Starting from the action optimization of temperature control unit and air flow control unit, pesticide molecules volatilizing from solution are efficiently captured by substrate and generate real-time SERS signals by a hand-held Raman spectrometer, and the sensor system based on HT-SPME-SERS was finally established. A novel SERS substrate of Cu@rGO@Ag was developed as HT-SPME-SERS material, where reduced graphene oxide (rGO) enriched pesticide molecules by π-π stacking. A superior detection sensitivity brought by the ultra-high enhancement effect of Cu@rGO@Ag substrate was obtained. A good linear relationship between Raman intensity and isocarbophos concentration was obtained and the limit of detection (LOD) was as low as 0.00451 ppm. The detection results obtained from the sensor system have been verified by gas chromatography-mass spectrometer (GC-MS), showing its great application potential for the safety of agricultural products.