The hydrates of bromine monoxide, BrO(H2O)(n,) n = 1-4, have been studied by means of ab initio calculations at the B3LYP/aug-cc-pVTZ level of theory. These systems could be formed in the troposphere and participate in chemical reactions involved in the depletion of ozone. Several conformations are obtained and discussed for each of the hydrates mentioned. Two rather different intermolecular interactions are found, namely, conventional hydrogen bonding and Br center dot center dot center dot O associations. In contrast with a more traditional point of view in which hydrogen bonds could be assumed as the preferential interaction for the formation of these complexes, it is the Br center dot center dot center dot O association which yields the most stable conformations. Equilibrium geometries, harmonic frequencies, and relative energies have been calculated for the bromine monoxide hydrates for the first time. The theoretical binding energies indicate that the stabilization of the hydrates increases with the number of water molecules added. Cooperative effects are suggested to play a significant role in this stabilization. An analysis of relevant properties depending on the electron density in the bond critical points of the Br center dot center dot center dot O associations has been done for the first time, showing characteristic features of this interaction in comparison with the hydrogen bonds formed.