The gas-phase reaction between HOSO and NO(2) was examined using density functional theory. Geometry optimizations and frequency computations were performed at the B3LYP/6-311++G(2df,2pd) level of theory for all minimum species and transition states. The ground-state potential energy surface, including activation energies and enthalpies, were calculated using the ab initio CBS-QB3 composite method. The results suggest that the addition of HOSO and NO(2) leads to two possible intermediates, HOS(O)NO(2) and HOS(O)ONO, without any energy barrier. The HOS(O)NO(2) easily decomposes into HONO + SO(2) through the low energy product complex HONO···SO(2), whereas the HOS(O)ONO dissociates to HOSO(2) + NO products. This latter dissociation is preferred from the isomerization of the HOS(O)ONO to HOS(NO)O(2). Also, HOS(O)NO(2) isomerization to HOS(O)ONO is hindered due to the presence of a large energy barrier. From the thermodynamic aspect, the main products in the title reaction are HONO + SO(2), whereas HOSO(2) + NO are expected as a minor products.