The lower gas sensitivity, humidity dependence of the gas sensing properties, and long recovery times of room-temperature gas sensors severely limit their applications. Herein, to address these issues, a series of 3D inverse opal (IO) In₂O₃-ZnO heterogeneous composite microspheres (HCMs) are fabricated by ultrasonic spray pyrolysis (USP) employing self-assembled sulfonated polystyrene (S-PS) spheres as a sacrificial template. The 3D IO In₂O₃-ZnO HCMs possess highly ordered 3D inverse opal structures and bimodal (meso-scale and macro-scale) pores, which can provide large accessible surface areas and rapid mass transfer, resulting in enhanced gas sensing characteristics. Furthermore, the 3D IO architecture and n-n heterojunctions can extend the photoabsorption range to the visible light area, effectively prolonging the lifetimes of photo-generated charge carriers, and can increase separation of visible light-generated charges. As a result, the as-prepared 3D IO In₂O₃-ZnO HCMs deliver excellent NO₂sensing performance under visible light irradiation at room temperature, such as high sensitivity (Rgas/Rair = 54.3 to 5 ppm NO₂), low detection limit (250 ppb), fast recovery time (188 s), excellent selectivity and humidity independence. These enhanced photo-electronic gas sensing properties are attributed to the combination of highly ordered 3D IO microspheres and In₂O₃-ZnO heterogeneous composites