Rapid reactions of carboxylic acids with Criegee intermediates provide efficient gas phase removal processes and are proposed to trigger the formation of new molecular compounds, which are implicated in the growth of atmospheric aerosols. The new adducts formed in these reactions are known as hydroperoxide esters and are predicted to be condensable, with lower vapor pressures than the reactants. We report here the direct detection of hydroperoxyethyl formate (HOOCH(CH3)OCHO) formed in the gas phase reaction between the methyl substituted Criegee intermediate, CH3CHOO, and formic acid. Two different isomers of this hydroperoxide ester have been observed using the combination of pulsed Fourier-transform microwave spectroscopy with isotopic substitution experiments and high-level quantum chemical calculations. The identification of hydroperoxyethyl formate as the main nascent product of the CH3CHOO and HCOOH reaction differs from previous results that reported the formation of vinyl hydroperoxide as the reaction product of this reaction.