Combining dissimilar transition metal oxides (TMOs) into artificial heterostructures enables to create electronic interface systems with new electronic properties that do not exist in bulk. A detailed understanding of how such interfaces can be used to tailor physical properties requires characterization techniques capable to yield interface sensitive spectroscopic information with monolayer resolution. In this regard resonant x-ray reflectivity (RXR) provides a unique experimental tool to achieve exactly this. It yields the element specific electronic depth profiles in a non-destructive manner. Here, using a YBa₂Cu₃O_7-δ (YBCO) thin film, we demonstrate that RXR is further capable to deliver site selectivity. By applying a new analysis scheme to RXR, which takes the atomic structure of the material into account, together with information of the local charge anisotropy of the resonant ions, we obtained spectroscopic information from the different Cu sites (e.g., chain and plane) throughout the film profile. While most of the film behaves bulk-like, we observe that the Cu-chains at the surface show characteristics of electron doping, whereas the Cu-planes closest to the surface exhibit an orbital reconstruction similar to that observed at La_1-x Ca _x MnO₃/YBCO interfaces.