Hydrophobically modified sodium alginate stabilizes benzene in water emulsions. The stability of the emulsion is related to the interface properties at the mesoscopic scale, but the details of the polymer adsorption, conformation and organization at oil/water interfaces at the microscopic scale remain largely elusive. In this study, hydrophobically modified sodium alginate was used as a representative of amphiphilic polymers for prediction of distribution of HMSA at the oil/water interface by coarse-grained molecular dynamics simulation. The result showed that driven by the interaction energy between the hydrophobic segment and benzene, HMSA will actively accumulate at the oil/water interface. The HMSA molecules parallel to the oil/water interface prevent the hydrophobic segments in the micelles from approaching the oil/water interface, so that the micelles can exist stably by steric hindrance. This study would be helpful to understand the aggregation behavior of amphiphilic polymers at the oil/water interface, these results can have applications in diverse sectors such as drug, food industry, where polymers are used to stabilize emulsions.