A process for the production of chlorine dioxide by reacting in a reaction vessel an alkali metal chlorate, mineral acid and a reducing agent in such proportions that chlorine dioxide is produced in a reaction medium which is maintained at a temperature of from about 50.degree. C. to about 100.degree. C. and at an acidity within a range of from about 5N to about 11N. The reaction medium is subjected to subatmospheric pressure sufficient for evaporating water, a mixture of chlorine dioxide, oxgen and water vapour being withdrawn from an evaporation zone in the reaction vessel, and alkali metal sulfate being precipitated in a crystallization zone in the reaction vessel. As the reducing agent hydrogen peroxide is used.