The use of solid adsorbents to separate and remove pollutants from the environment is an effective and common method for environmental pollution control, in which functional adsorbents based on inorganic materials are more widely used. Silica nanoparticles feature good stability, easy modification, low cost and environmental friendliness, thus leading to widespread potential in the treatment of environmental pollutants. Compared with traditional silica nanoparticles, fibrous silica spheres have the advantages of large specific surface area and open pores, which can provide more effective adsorption sites and ensure that pore channels are not easily blocked during practical applications, and thus show more potential in adsorption applications. In this paper, the synthesis and preparation of fibrous silica spheres, in particular, the regulation of structural parameters, are summarized and analyzed based on the reported researches and the works of our group. The application of functional fibrous silica spheres in the adsorption and separation of environmental pollutants in recent years is then reviewed and summarized following the analysis of recent progress in the treatment of heavy metals, organics, radionuclides and other environmental pollutants. Finally, the application of functional fibrous silicon sphere in the field of adsorption and separation is prospected from the points of view of limitations of fiber-like silicon sphere synthesis and application potentials.