The interfacial properties of reactive powder concretes (RPCs), other known as ultra-high performance concrete (UHPC), containing steel slag powder and ultra fine fly ash are studied in this paper. The microstrctural characterization of interfacial transition zones (ITZs), including the aggregate-cement paste interfacial zone and the steel fiber-paste interfacial zone, is investigated by SEM. The microhardness of the aggregate-paste ITZ and the steel slag-paste ITZ is studied and the bond strength of steel fiber in matrix is tested through fiber pullout tests. The results indicate that the microhardness of the steel slag-paste ITZ is slightly higher than that of the aggregate-paste ITZ, which implies the advantage of the substitution of quartz powder with steel slag powder in preparation of RPCs to some degrees. Moreover, the hardness of these two ITZs is higher than that of the hardened paste. A certain amount of hydration products has been observed exsiting on the surface of steel fiber by SEM and the bond strength of steel fiber-martix is up to 9.3MPa. These interfical properties are definitely critical to obtain high performance of UHPCs containing steel slag powder and fly ash.