Significance Copper-based (cuprate) oxides are not only the original but also one of the best-studied families of “high-temperature” superconductors. With nominally identical crystal structure and electron count, nickel-based (nickelate) compounds have been widely pursued for decades as a possible analog to the cuprates. The recent demonstration of superconductivity in nickelate thin films has provided an experimental platform to explore the possible connections between the copper- and nickel-based superconductors. Here, we perform highly localized spectroscopic measurements to reveal a number of key differences between the two systems, particularly with regard to the hybridization between the O and metal (Cu or Ni) orbitals.