Straw return can improve soil quality and change the mobility and bioavailability of pollutants in soil. Elevated cadmium (Cd) contents in farmland soils were often reported. However, the impacts of straw-derived dissolved organic matter (DOM) on Cd speciation in soil remain poorly understood. In this study, the effects of straw return and moisture condition on temporal changes of DOM composition and Cd speciation in farmland soils were explored through a laboratory incubation experiment. The humified components of DOM were negatively correlated with exchangeable, carbonate-bound, and Fe-Mn oxide-bound Cd (p < 0.01), while its protein-like component was negatively correlated with residual Cd (p < 0.01). It was found that selected fluorescence parameters could be used to predict temporal changes of Cd geochemical fractions. Straw addition led to increases in soil DOM content during the first three days of the incubation. Flooding should be avoided in the first three days following the straw application to reduce the risk of DOM-facilitated Cd mobilization.