The powder-based photocatalytic material is often difficult on wide application and then loaded on a matrix for separating conveniently from the liquid. Submerged photocatalysts may not take advantage of the light energy adequately. Thus, this boundedness may reduce their utilization and potentially cause the secondary pollution on the environment. In this paper, the micron-sized silica sphere is used as a floating substrate, and the visible-light-driven photocatalytic material iodine oxygen bismuth is prepared onto the hollow silica microspheres. The composite spheres as the visible-light-driven photocatalytic material have been characterized by XPS, XRD, SEM, EDX, PL, etc. It confirmed that BiOI combined on the SiO2 microsphere (mSiO2) by Bi-O-Si. The photogenerated electrons of the composite have a low probability of recombination and have a narrow band energy (1.82 eV). The composite was used to photodegrade diesel-containing wastewater and rhodamine B, and the superoxide group (·O2−) was found to be the main degradation active factor. And by GC–MS test, it is known that the superoxide group (·O2−) can degrade long-chain alkanes into short chains or form branches. Detailed studies on the acute exposure experiments of Vibrio qinghaiensis sp.-Q67 and zebrafish embryos showed that the composites can effectively reduce the toxicity of BiOI and mSiO2.