A new procedure to produce the BrO2 transient species allowed time-resolved UV-vis spectra that show a structured band (lambda(max) = 502 nm) in dichloromethane to be obtained. In water, because of the increase of the dielectric constant, the lambda(max) presents a blue shift to 474 nm and the species decomposes much faster. The time-resolved spectra show evidence for its equilibrium with a nonidentified colorless form. This route opens new possibilities to the study this species in solution.