Scanning tunnelling spectroscopy (STS) of thin Fe films on W(110) shows that theelectronic structures of magnetic domains and domain walls are different. Thisexperimental result is explained on the basis of first-principles calculations. Adetailed analysis reveals that the spin–orbit induced mixing between minority dxy+xz andminority dz2spin states depends on the magnetization direction and changes the local densityof states in the vacuum detectable by STS. The effect scales in second or fourthorder with the magnetization angle relative to the easy axis. Our finding impliesthat nanometre-scale magnetic structure information can be obtained even byusing non-magnetic probe tips. Magnetization dependent measurements show thatthe canting of adjacent spins has no major influence on the electronic structure ofthe sample.