The present study proposes a new approach for direct CO2 conversion using primary radicals from water irradiation. In order to ensure reduction of CO2 into CO2 -• by all the hydrated electrons, we use formate ions to scavenge simultaneously the parent oxidizing radicals H • and OH • producing the same transient CO2 -• radicals. Conditions are optimized to obtain the highest conversion yield of CO2. The goal is achieved under mild conditions of room temperature, neutral pH and 1 atm of CO2 pressure. All the available radicals are exploited for selectively converting CO2 into oxalate that is accompanied by H2 evolution. The mechanism presented accounts for the results and also sheds light on the data in the literature. The radiolytic approach is a mild and scalable route of direct CO2 capture at the source in industry and the products, oxalate salt and H2, can be easily separated.