The reactions of HO 2 with FCHO and ClCHO have been theoretically investigated by combining beyond-CCSD(T) electronic structure benchmarks, validated density functional theory, and canonical variational transition state theory with small-curvature tunneling, coupledtorsions anharmonicity, and high-frequency anharmonicity. This investigation explores three different reaction mechanisms: radical addition plus a hydrogen transfer, radical addition, and hydrogen abstraction. The calculated results show that the dominant reaction pathway is the terminal oxygen atom of HO 2 added to the carbon atom of XCHO (X = F, Cl) and simultaneously the hydrogen atom of HO 2 transferred to the oxygen atom of the C=O group in XCHO. The reaction barriers of the other reaction pathways are so high that these processes are negligible in the atmosphere. Although the barrier height of the dominant reaction pathway in the HO 2 + FCHO reaction is 0.61 kcal/mol higher than that of the corresponding HO 2 + ClCHO reaction, the HO 2 + FCHO reaction is faster than the HO 2 + ClCHO reaction because the variational effects of HO 2 + ClCHO is more obvious than that of the HO 2 + FCHO. The present results show that the HO 2 + FCHO reaction may be important in the atmosphere. The present results should be useful in evaluating the atmospheric fate of XCHO (X = F, Cl).