Nuclear magnetic resonance (NMR) is a powerful tool to study the local stru
cture of ultrathin magnetic films and multilayers. This is demonstrated wit
h an NMR study of ultrathin molecular beam epitaxy-grown Co layers on singl
e-crystal Cu(111), Cu(110) and Pd(111) substrates. Co on Cu(111) results in
a mixture of fcc and hcp phases and the Cu(111)/Co interface is near to pe
rfect. Co on Cu(110) grows mainly fee in long stripe-shaped islands with ro
ugh Co/Cu interfaces. Finally, Co on Pd(111) gives a (111)-oriented fcc str
ucture. The top surface is flat, but the Pd(111)/Co surface is intermixed.