The effects of H2O addition on downstream interaction in counterflow premixed CO/O2 flames are investigated by varying the global strain rate (ag) and CO mole fractions (XCO,L, XCO,U) in the lower and upper nozzles, respectively. For interacting premixed CO/O2 flames, the flammable region is very narrow such that the flames cannot be sustained for ag > 11.75 s−1 When 1.0% vol H2O is added to O2/CO2 mixtures, the flammable region is appreciably extended. At low strain rate, the lean-lean and rich-rich extinction boundaries show strong and weak interactions similar to those observed previously in hydrocarbon fuels. The flammable lean-lean and rich-rich regions gradually shrink with the increase of ag. When XCO,U is small for asymmetric lean double flames at low strain rate, the extinction boundary exhibits weak interaction behavior, where the weaker flame is parasitic to the stronger flame by XCO,L. The stronger flame experiences heat loss to the weaker flame. As the strain increases, the reaction cannot be completed due to the reduction in the flow time. The thermal energy loss by incomplete reaction leads to the flame extinction. This effect changes the qualitative nature of extinction boundary as strain rate increases, resulting in the extinction boundary having only the strong interaction mode having near constant (XCO,L + XCO,U) and bending toward larger XCO,L, and eventually forming an island shape at higher strain rate. The local equilibrium temperature (LET) concept is introduced to explain these flame extinction mechanisms. Local temperature behaviors are well explained by investigating major reaction contributions to heat release rate. In all cases, LET decreases by the effect of preferential diffusion because of the Lewis number of deficient reactant being larger than unity. For asymmetric double flames, conductive heat transfer (CHT) from the stronger to weaker flame reduces the LET of the stronger flame. Flame extinction mechanism can be explained by introducing a loss ratio. For CO/O2 flames, the effects of incomplete reaction as well as preferential diffusion and CHT lead to flame extinction. For (CO/O2 + 1.0% H2O) flames with the increase of strain rate, thermal energy loss by incomplete reaction becomes appreciable, as compared with the effects of preferential diffusion and CHT.