Atomic clusters consist of a finite number of atoms and exhibit distinctive electronic structures intermediate between those of isolated atoms and bulk materials. Their physicochemical properties are highly sensitive to size, geometry, and charge state, making them valuable platforms for probing microscopic reaction mechanisms and tuning catalytic performance. However, securely immobilizing clusters while preserving a specific charge state remains a key challenge in developing cluster-based functional systems. This work focuses on the interactions between positively charged gold clusters and insulating substrates. By introducing neutral chemical anchoring sites through surface functionalization, we explore strategies for immobilizing individual clusters while keeping them spatially isolated from one another. First-principles calculations are employed to investigate cluster–surface bonding, charge redistribution, and structural stability, and to examine how the local coordination environment affects charge retention and cluster migration. This study aims to provide a theoretical basis for designing materials that combine short-term charge retention with long-term positional stability in gaseous environments at room temperature and atmospheric pressure, laying the groundwork for single-cluster catalysis with well-defined active sites and tunable electronic states.