1. The formation of bismuth(II) and bismuth(IV) under the action of ionizing radiation on hydrochloric acid solutions of bismuth(III) has been shown by low-temperature and pulse radiolysis. The kinetics of bismuth(IV) disappearance at 300°K have a complex nature and would seem to be caused both by the disproportionation of bismuth (IV) and the reaction of bismuth(IV) with bismuth(II), which leads to bismuth(III). 2. The properties of bismuth (IV), which is formed from the reaction of Cl2 with bismuth (III) agree with previously established relationships on the variation in optical transition energies and the unpaired electron density at the s atomic orbital of the ion for the series of isoelectronic ions mercury (I), thallium (II), lead (III), and bismuth (IV) in the2S1/2 state.