In recent years, during industrial development, the expanding discharge of harmful metallic ions from different industrial wastes (such as arsenic, barium, cadmium, chromium, copper, lead, mercury, nickel, selenium, silver, or zinc) into different water bodies has caused serious concern, with one of the problematic elements being represented by selenium (Se) ions. Selenium represents an essential microelement for human life and plays a vital role in human metabolism. In the human body, this element acts as a powerful antioxidant, being able to reduce the risk of the development of some cancers. Selenium is distributed in the environment in the form of selenate (SeO42–) and selenite (SeO32–), which are the result of natural/anthropogenic activities. Experimental data proved that both forms present some toxicity. In this context, in the last decade, only several studies regarding selenium’s removal from aqueous solutions have been conducted. Therefore, in the present study, we aim to use the sol–gel synthesis method to prepare a nanocomposite adsorbent material starting from sodium fluoride, silica, and iron oxide matrices (SiO2/Fe(acac)3/NaF), and to further test it for selenite adsorption. After preparation, the adsorbent material was characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). The mechanism associated with the selenium adsorption process has been established based on kinetic, thermodynamic, and equilibrium studies. Pseudo second order is the kinetic model that best describes the obtained experimental data. Also, from the intraparticle diffusion study, it was observed that with increasing temperature the value of the diffusion constant, Kdiff, also increases. Sips isotherm was found to best describe the experimental data obtained, the maximum adsorption capacity being ~6.00 mg Se(IV) per g of adsorbent material. From a thermodynamic point of view, parameters such as ΔG0, ΔH0, and ΔS0were evaluated, proving that the process studied is a physical one.