A blending technique was studied in order to widen the applications of aramid-silicone multiblock copolymer (PAS). A PAS/aramid blend film was prepared and the characterization of the surfaces was investigated. The two-phase nature of poly(dimethylsiloxane) (PDMS) and the aromatic polyamide (aramid) multiblock copolymer (PAS) were clarified in part by evaluating the surface enrichment in PAS/aramid blend films. There were no significant differences among the PASs as additives; however, the PASs were able to alter the aramid surface to that of silicone, even though they were used at low concentration. The atomic force microscopy observation suggested that the mobility of the silicone segment that existed on the surface was restricted by the associated aramid segments.