A strong low-energy shake-up satellite for CO adsorbed on Pd is observed. The occurrence of the satellite is established for the CO/1 ML Pd/Mo(110) system at a coverage where CO adsorbs exclusively on-top. Comparisons with CO adsorbed on Pd single-crystal surfaces and small supported Pd particles indicate that the strongly increased satellite intensity is due to the decreased CO-Pd interaction strength for on-top adsorbed CO. This can be used to get further insight into the structure and bonding properties of the adsorbate system. Since a low-energy shake-up feature may be misinterpreted as a chemically shifted component, the conclusion is that great care has to be taken in the evaluation of adsorbate core-level spectra for systems with large variations in adsorption strength depending on the adsorbate sites. Large variations in the CO site distribution may furthermore occur depending on the nature of the Pd substrate: Adsorption of CO on 1 ML Pd/Mo(110) leads to an overlayer dominated by an on-top species and, likewise, the CO overlayer formed on small Pd particles after large doses has a large fraction of on-top bonded species. This is in strong contrast to Pd single-crystal surfaces, where CO adsorbed in more highly coordinated sites is abundant.