Experimental results show that the exchange coupling field (Hex) of NiFe/FeMn for Ta/NiFe/FeMn/ Ta multilayers is higher than that for spin-valve multilayers Ta/NiFe/Cu/NiFe/FeMn/Ta. In order to find out the reason, the composition and chemical states at the surface of Ta(12 nm)/NiFe(7 nm), Ta(12 nm)/NiFe(7 nm)/Cu(4 nm), and Ta(12 nm)/NiFe(7 nm)/Cu(3 nm)/NiFe(5 nm) were studied using x-ray photoelectron spectroscopy. The results show that no elements from lower layers float out or segregate to the surface in the first and second samples. However, Cu atoms segregate to the surface of Ta(12 nm)/NiFe(7 nm)/Cu(3 nm)/NiFe(5 nm) multilayers,ie., Cu atoms segregate to the NiFe/FeMn interface for Ta/NiFe/Cu/NiFe/FeMn/Ta multilayers.We believe that the presence of Cu atoms at the interface of NiFe/FeMn is one of the important factors which causes the exchange coupling field (Hex) of Ta/NiFe/Cu/NiFe/FeMn/Ta to be weaker than that of Ta/NiFe/FeMn/Ta.