X-ray photoelectron spectroscopy (XPS) spectra from solid samples are conventionally referenced to the spectrometer Fermi level (FL). While, in the case of metallic samples, alignment of the sample and the spectrometer FLs can be directly verified from the measured Fermi edge position, thus allowing to assess the surface electrical potential, this is not a workable option for insulators. When applied, it generates a large spread in reported binding energy values that often exceed involved chemical shifts. By depositing insulating amorphous alumina thin films on a variety of conducting substrates with different work functions, we show not only that FL referencing fails but also that the Al2O3 energy levels align instead to the vacuum level, as postulated in the early days of XPS. Based on these model experiments that can be repeated for all sorts of thin-film insulators, a solution to the binding energy reference problem is proposed for reliable assessment of chemical bonding.