The electronic structure of a Cu monolayer buried in Ni fcc(100) is studied by means of x-ray emission and absorption spectroscopies in combination with first principles calculations. The local character of the x-ray probes allows us to investigate changes in the chemical interaction for these ultrathin film systems. In comparison to bulk Cu, the occupied d states of a buried Cu monolayer, as mapped in the x-ray emission spectrum, remain mostly unaltered. The absorption spectrum on the other hand shows that the empty states of the buried Cu monolayer are modified, and instead resemble the unoccupied electronic density of bulk Ni. These findings agree well with our first principle electronic structure calculations and the results are interpreted in terms of short- and long-range hybridization.