Exploring a covalent organic framework (COF) material as an efficient metal-free photocatalyst and as an adsorbent for the removal of pollutants from contaminated water is very challenging in the context of sustainable chemistry. Herein, we report a new porous crystalline COF, C6-TRZ-TPA COF, via segregation of donor-acceptor moieties through the extended Schiff base condensation between tris(4-formylphenyl)amine and 4,4',4″-(1,3,5-triazine-2,4,6-triyl)trianiline. This COF displayed a Brunauer-Emmett-Teller (BET) surface area of 1058 m2 g-1 with a pore volume of 0.73 cc g-1. Again, extended π-conjugation, the presence of heteroatoms throughout the framework, and a narrow band gap of 2.2 eV, all these features collectively work for the environmental remediation in two different perspectives: it could harness solar energy for environmental clean-up, where the COF has been explored as a robust metal-free photocatalyst for wastewater treatment and as an adsorbent for iodine capture. In our endeavor of wastewater treatment, we have conducted the photodegradation of rose bengal (RB) and methylene blue (MB) as model pollutants since these are extremely toxic, are health hazard, and bioaccumulative in nature. The catalyst C6-TRZ-TPA COF showed a very high catalytic efficiency of 99% towards the degradation of 250 parts per million (ppm) of RB solution in 80 min under visible light irradiation with the rate constant of 0.05 min-1. Further, C6-TRZ-TPA COF is found to be an excellent adsorbent as it efficiently adsorbed radioactive iodine from its solution as well as from the vapor phase. The material exhibits a very rapid iodine capturing tendency with an outstanding iodine vapor uptake capacity of 4832 mg g-1.