The invention includes convenient methods of preparing: (1) highly concentrated liquid bromine-containing biocidal solutions, (2) highly concentrated mixed halogen liquid bromine and chlorine-containing biocidal solutions, and (3) high-activity bromine-containing biocidal solids, all having excellent physical and chemical stability. One method yields solutions that have concentrations of bromine in excess of 18% as Br.sub.2 (8% as Cl.sub.2) in which the mole ratio of hydroxide ion to hydrogen ion source is at least 1.9:1. Another method employs elemental bromine in conjunction with a solid organic or inorganic halogenating agent to yield halogen solutions at concentrations greater than 22.9% as Br.sub.2 (10.2% as Cl.sub.2). This method can be performed under conditions that exceed the solubility of the active ingredient such that it crystallizes and is recovered as a hydrated or anhydrous salt in good yield.