Saturated aqueous chloroform solutions (0.07 M) with pH ranging from 0.8 to 12.6 have been irradiated with 60Co γ-radiation in the presence and absence of air. G(Cl− + ClO−) increases with increasing pH in the pH range 1–3 (aerated solutions) or 3–6 (deaerated solutions) and again at pH greater than 10.5. The variation in yield from aerated solutions in the region pH 1–3 is attributed to competition between chloroform and hydrogen ions for hydrated electrons. However, such competition cannot account for the pH effect observed in deaerated solutions between pH 3 and 6. Increased yields from both aerated and deaerated solutions at high pH are attributed to the formation of O− by reaction of hydroxyl radicals and hydroxide ions. Formic acid and oxalic acid have been identified as minor products when aerated chloroform solutions are irradiated.