Tin dioxide is important gas sensor material and has wide applications in the detection of toxic gases and volatile organic compounds. Here, we synthesized a 3D laminated structural CuO/SnO2 material possessing p-n heterostructures. The morphology and structure were characterized by XRD, SEM, TEM and XPS techniques and the sensing properties were investigated for the detection of triethylamine (TEA). The results indicate that 3D laminated CuO/SnO2 material, assembled by lamellae consisting of ordered nanoparticles, exhibit an enhanced sensing performance compared with SnO2, and notably, CuO/SnO2 with size less than 1μm has obvious high selectivity in the detection of 100 ppm TEA. Particularly, it has a high response and stability to 1 and 5 ppm TEA (S is 8 and 33), and that is higher than SnO2 material, suggesting 3D laminated CuO/SnO2 is an effective candidate material served as sensor platform to detect low-concentration amines.