The remediation of paddy soils co-contaminated with As and Cd is tricky. It is difficult to decrease Cd and As availability simultaneously due to their opposite geochemical characteristics. Finding the optimal trade-off relationship between As and Cd availability in paddy soils is a significant task that is necessary to guide the construction of water management measures. This study investigated the dissolution characteristics of As, Cd, Fe, Mn, DOC, DOM, and various As and Cd fractions in soils via the microcosm system and calculated the optimal trade-off value for available As and Cd in porewater. The results showed that the total As in porewater increased rapidly when the soil Eh was reduced to −104 mV. Meanwhile, the total Cd in porewater decreased dramatically when the soil Eh was below 62 mV. Under flooding and drainage conditions, Fe/Mn (oxyhydro)oxides play a vital role in regulating Cd dissolution in paddy soils, while Fe/Mn (oxyhydro)oxides organically bind sulfide together to determine the dissolution of As. Additionally, the optimal pe + pH response to the minimum trade-off value of available As and Cd in porewater was found to be 6.6, which indicates a moderate reduction status. Therefore, further research should apply the optimal pe + pH to construct water management measures to safely utilize co-contaminated paddy fields.