Motivated with the continued demand for developing quality material showing better response for the efficient removal of organo-amphiphilic toxicants, we have demonstrated the growth of three-dimensional polymer organic framework-a covalent crosslinked polymer C2B derived via photon triggered thiol-alkene click reaction.Instrumentation techniques such as nuclear magnetic resonance, thermogravimetric analysis, and fourier transform infrared spectroscopy were used for the characterization. FESEM and Cryo-SEM analysis were done to analyze the morphology of the resin. The adsorption and release experiments were done with ultraviolet-visible spectroscopic technique. The polymer C2B derived from polyolefin and tetrathiol via thiol-alkene photoclick reaction showed efficiency toward adsorption of organoamphiphilic contaminants such as dioxane, dimethylformamide, fluorescein, and rhodamine B (RH). Even the material selectively showed the efficient release of toxicant-RH. Moreover, it can be reused over cycles. This makes the polymer C2B as potential candidate to be commercially viable for textile industries.