AbstractIntra‐ and inter‐molecular bromine migrations in bromophenols occur in the presence of catalytic amounts of aluminium phenoxides or proton acids (such as sulfuric and trifluoromethanesulfonic acid) at temperatures between 80 and 180°C. Under these conditions onlyorthoandparapositions are involved; nometa‐bromophenols are formed.The equilibrium constants for theortho‐orthotranssubstitution (Kx= [2‐bromo‐4‐X‐phenol]2/[2,6‐dibromo‐4‐X‐phenol] [4‐X‐phenol = 15 ± 3) are independent of substituents in theparaposition. The equilibrium constants for theortho‐paraisomerization are calculated (R2/4= [2‐bromophenol]/[4‐bromophenol]= 1.9±0.3; R2,6/2,4= [2,6‐dibromophenol]/[2,4‐dibromophenol]= 0.34± 0.04). Kinetic data ‐ some of them suggesting second‐order