Despite the various attractive properties of γ-pyrones, there are still some deficiencies in their synthetic approaches such as lower atom economy, multistep processes, and prefunctionalization of the reagents. In this work, an efficient and simple (CF3CO)2O/CF3SO3H-mediated "one-pot" approach was realized to produce γ-pyrones by applying aromatic ketones/heteroarenes and carboxylic acids as the starting materials. The target products were isolated in moderate to excellent yields. The reaction mechanism was studied by density functional theory calculational methods. The results of experimental and theoretical investigations not only helped us explain the reason of high selectivity formation of β-diketones but also proved that 1,3,5-ketones might be important intermediates for the cyclization to afford γ-pyrones.