Sliding of alumina (87%) pins against a hardened steel disk over a range of pressures (3.3–30.0 MPa) and speeds (0.1–12.0 ms-1) has been studied. Four different regions (R1, R2, R3, and R4) of friction as a function of speed have been identified. R1 and R3 exhibit single-valued friction while in R2 and R4 the friction exhibits dual behavior. The speed range over which these regions prevail is sensitive to the pressure. R1 and R2 are low-speed and low-temperature regions, and in both, metal transfer and formation and compaction of y-Fe2O3 occur. R3 and R4 are associated with high speeds and high interface temperatures. Formation of FeO, FeAl2O4, and FeAlO3 has been observed. The implications of the tribochemical interactions on friction and wear characteristics are discussed.