We explore the local electronic signatures of molecular adsorption at coordinatively unsaturated binding sites in the metal organic framework Mg-MOF-74 using X-ray spectroscopy and first-principles calculations. In situ measurements at the Mg K-edge reveal distinct pre-edge absorption features associated with the unique, open coordination of the Mg sites which are suppressed upon adsorption of CO2 and N,N'-dimethylformamide. Density functional theory shows that these spectral changes arise from modifications of local symmetry around the Mg sites upon gas uptake and are strongly dependent on the metal-adsorbate binding strength. The expanded MOP Mg-2(dobpdc) displays the same behavior upon adsorption of CO2 and N,N'-dimethylethylenediamine. Similar sensitivity to local symmetry is expected for any open metal site, making X-ray spectroscopy an ideal tool for examining adsorption in such MOFs. Qualitative agreement between ambient-temperature experimental and 0 K theoretical spectra is good, with minor discrepancies thought to result from framework vibrational motion.