Iodine and bromine inclusion compounds were easily prepared by gas diffusion of the halogens using finely powdered CB[6]. A brown powder consisting of I2–CB[6]·4H2O and an orange one of (Br2)4–CB[6]·10H2O were employed in several different reactions. I2–CB[6] can be used in catalytic reactions giving yields comparable to those reported in the literature. Br2–CB[6] was effectively applied in electrophilic bromination of benzene and formation of bromohydrin. However, the radical substitution at cyclohexene could not be performed. Overall, based on these results, several applications can be envisioned for these complexes.