Herein, the snowball flower-like g-C3N4/ZnFe2O4 mesoporous hollow microspheres, in which two-dimensional (2D) g-C3N4 nanolayers were loaded onto the surface of ZnFe2O4 hollow microspheres, were constructed by a simple solid phase reaction. The effect of the g-C3N4 concentration on the structure, morphology and gas-sensing performance of the g-C3N4/ZnFe2O4 composites had been explored. On the basis of gas sensitivity test results, the composites owned lower working temperature (160 ℃) and better selectivity toward TEA in comparison with pure ZnFe2O4. Notably, the sensor based on the g-C3N4/ZnFe2O4-15 hollow microspheres (adding 15 ml of g-C3N4 aqueous solution) exhibited outstanding sensing properties, including superior response (18.3) toward 100 ppm TEA at optimum work temperature of 160 ℃, speedy response-recovery time (33, 30 s) and outstanding stability. And the sensor maintained high response of 4.3 to low concentration TEA (5 ppm). The improved gas-sensing performance of the composites could be attributed to the porous ZnFe2O4 hollow microspheres loaded by 2D g-C3N4 nanolayers with large specific surface area and the heterostructure formed between them. Hence, a potential application of the g-C3N4/ZnFe2O4 microspheres might be achieved in detecting TEA at a low optimum work temperature.