We carried out reactions of methyl-substituted cyclohexenes and alpha -pinene with ozone in air and elucidated the mechanisms of formation of the minor products (peroxides and formic acid). Peroxyacetic acid was formed only from the cyclohexenes with a methyl group on the double bond, whereas formic acid was produced in higher yields from the cyclohexenes without a methyl group on the double bond. These differences in product yields allowed us to elucidate the mechanism of formation of the products.