An understanding of the radiation-induced effects in groundwater is essential to evaluate the safe geological disposal of spent fuel. In groundwater, the bicarbonate ion is the predominant and common anion; this work investigated radiation-induced chemical reactions of (bi)carbonate aqueous solutions with steady-state irradiation and pulse radiolysis methods. Aqueous solutions of sodium (bi)carbonate as high as 50 mmoldm-3 were used. The formation of formate, oxalate, and H2O2 were measured under different conditions. A complete set of reaction steps and reliable kinetic data for the radiolysis of (bi)carbonate aqueous solutions at ionic strength close to the groundwater were proposed. Kinetic calculations were completed based on the proposed reaction steps and the kinetic data obtained in the present work. The results from the calculation are in good agreement with the experimental results. With these proposed reaction steps and kinetic data, computer simulation can be performed to predict the yield of radiolytic products of (bi)carbonate aqueous solutions as a function of irradiation time and used to evaluate the safety of geological disposal options of spent fuel.