In recent years, people have focused on the development of simple and efficient heterogeneous catalysts for the styrene epoxidation reaction. In this work, a FeCo double metal cyanide (DMC) was modified with C1 to C6 linear alcohols, and the prepared materials were used to catalyze the reaction of styrene epoxidation in various solvents. It is noteworthy that the styrene conversion is mainly affected by modification with alcohols, while the selectivity in styrene oxide (SO) is obviously influenced by the solvent. FeCo DMC along with MeOH exhibits the best catalytic performance, with a conversion rate of 96% and a SO selectivity of 86%, in N,N-dimethylformamide (DMF) solvent. Various physical and chemical methods were used to analyze the structures and compositions of the materials. To clarify the mechanism of the improvement, we set up an original approach to investigate the kinetics of the adsorption process between the oxidant and the catalyst, using isothermal titration calorimetry (ITC). The obtained results illustrate that the adsorption process of the oxidant on the surface of FeCo DMC can be dramatically promoted by the presence of MeOH. Such a difference in adsorption thus explains the significant improvement of its catalytic activity by modification with MeOH. This study thus provides a new fundamental understanding of DMC catalysts for the styrene epoxidation reaction.