Radical-mediated single carbonylation of alkyl iodides furnishing carboxylic acids proceeded in water using phosphinic acid as a radical initiator in the presence of a surfactant (CTAB). On the other hand, formation of double carbonylation product (alpha-keto carboxylic acid) along with single carbonylation product was observed for the first time, when the reaction was carried out in aqueous ethanol without any surfactants.