There is a strong and urgent need for efficient materials that can capture radioactive iodine atoms from nuclear waste. This work presents a novel strategy to develop porous materials for iodine capture by employing halogen bonding, mechanochemistry and crystal engineering. 3D halogen-bonded organic frameworks (XOFs) with guest-accessible permanent pores are exciting targets in crystal engineering for developing functional materials, and this work reports the first example of such a structure. The new-found XOF, namely TIEPE-DABCO, exhibits enhanced emission in the solid state and turn-off emission sensing of acid vapors and explosives like picric acid in nanomolar quantity. TIEPE-DABCO captures iodine from the gas phase (3.23 g g⁻¹ at 75 °C and 1.40 g g⁻¹ at rt), organic solvents (2.1 g g⁻¹), and aqueous solutions (1.8 g g⁻¹ in the pH range of 3–8); the latter with fast kinetics. The captured iodine can be retained for more than 7 days without any leaching, but readily released using methanol, when required. TIEPE-DABCO can be recycled for iodine capture several times without any loss of storage capacity. The results presented in this work demonstrate the potential of mechanochemical cocrystal engineering with halogen bonding as an approach to develop porous materials for iodine capture and sensing.