Heterogeneous photocatalytic technology based on semiconductors has been considered to be a green technology for environmental remeidation because it can use the solar energy. As a semiconductor visible light catalyst, ZnIn2S4 has attracted a lot of attention because of its narrow bandgap, strong absorption of visible light and unique catalytic properties. However, the disadvantages that the powders ZnIn2S4 are easy to aggregate and hard to separate make its photocatalytic efficiency limited. Besides, micro/nano powders are difficult to recycle, which tends to cause secondary pollution and increase the cost of photocatalysis inevitablely. In order to solve the disadvantages of the powder photocatalysts, floating substrates hollow glass microspheres (HGMs) are used as supporters for the coating of powder photocatalysts. Hollow glass microspheres, which are commonly used as floating-type carrier for photocatalysts due to their favorable properties of high chemical stability, low cost, lightweight mass, low thermal conductivity, hollow spherical morphology, good dispersibility and fluidity, are considered one of the most suitable supporters, and their combination are expected to show higher light utilization and collection efficiencies. In this research, the visible light photocatalyst ZnIn2S4 was coated on HGMs through a hydrothermal method at 160°C, which obtained HGM/ZnIn2S4 composite microspheres. The crystal structure, morphology and optical properties of the obtained composite microspheres were characterized by measurements such as X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectrum (XPS) and UV-Vis diffuse reflectance spectra (UV-Vis). The optimized conditions of ZnIn2S4 film coated on hollow glass microspheres were investigated by different pretreatment methods.such as alkali pretreatment, H2O2 activation and silane coupling modification. The results revealed that the activation of the HGMs through H2O2 and silane coupler angent KH550 showed better morphology of HGM/ZnIn2S4 composite microspheres with a nano-layered petal-like structure on the HGMs. Besides, HGM/ZnIn2S4 composite microspheres pretreated by silane coupling agent KH550 exhibited a higher hexagonal phase crystal structure compared with the H2O2 pretreated samples,and its band gap was estimated to be 2.37 eV from UV-vis absorbance spectrum,which showed that HGM/ZnIn2S4 composite microspheres exhibited good photocatalytic performance in the visible range. The HGM/ZnIn2S4 composite microspheres can not only maintain the high photocatalytic activity, but also overcome the disadvantages that nanoparticles powder are inclined to agglomeration in water.Furthermore, the degradation effect of Rhodamine B (RhB) under visble light were investigated through the as-prepared HGM/ZnIn2S4 composite microspheres. The results showed that the composite microspheres have good photocatalytic degradation effect on RhB, and the degradation of substrate RhB can reach 99.7 within 2 h. Finally, we proposed the possible growth mechanism of ZnIn2S4 film on HGMs and the formation of HGM/ZnIn2S4 composite microspheres. The precursor of ZnIn2S4 was firstly adsorbed on the surface of hollow glass microspheres by electrostatic adsorption. As the temperature of the reaction system was gradually increased, Zn(TAA) n 2+ and In(TAA) n 3+ generated at the same time can further combine in situ to yield numerous ZnIn2S4 nuclei. When the micronucleus of ZnIn2S4 was formed, the ZnIn2S4 nano-nucleus gradually deposited to form a layered petal structure, and then the HGM/ZnIn2S4 composite microspheres were prepared. The study showed a simple and reliable preparation condition and processe for ZnIn2S4 coated on hollow glass microspheres, which provides a promising application on photocatalytic field of the as prepared floating HGM/ZnIn2S4 composite microspheres, and it will be beneficial to explore the coating mechanism of ZnIn2S4 on glass-based carrier material.