Molecular chlorine (Cl2) is an important yet poorly understood trace constituent of the lower atmosphere. Although a number of mechanisms have been proposed for the conversion of particle-bound chloride (Cl-) to gas-phase Cl2, the detailed processes involved remain uncertain. Here, we show that reaction of dinitrogen pentoxide (N2O5) with aerosol-phase chloride yields Cl2 at low pH (<2) and should constitute an important halogen activation pathway in the atmosphere.