A detailed understanding of the interaction between molecules and 2D materials is crucial to implement molecular films into next-generation 2D material-organic hybrid devices effectively. In this regard, energy level alignment and charge transfer processes are particularly relevant. This work investigates the interplay between a hexagonal boron nitride (h-BN) monolayer on an Rh(111) single crystal and self-assembled C₆₀ thin films. The influence of the corrugated topography and electrostatic surface potential originating from the h-BN/Rh(111) Moiré superstructure on the electronic level alignment and charging characteristics of C₆₀ is being studied. A combination of scanning tunneling microscopy/spectroscopy (STM/STS) and a theoretical tight-binding approach is used to gain insight into the C₆₀ bandstructure formation and electronic decoupling of specific C₆₀. This decoupling results from adsorption site-dependent variations of the molecular energy level alignment, which controls the strength of intermolecular hybridization. The decoupling of specific C₆₀ enables the direct observation of single-electron charging processes via STS and Kelvin probe force microscopy. The charging of the C₆₀ is enabled by combining two gating mechanisms: the electrostatic surface potential of the monolayer h-BN/Rh(111) Moiré and the electric field of the STM tip.