To study the electronic structures of a compound, a combination of X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance (NMR) is employed to characterise the local structure in the molecule, providing atom-specific information and advantages . For example, combining core electron binding energies (CEBEs) measurable using O1s XPS (with the oxygen atom acting as a hydrogen acceptor) and chemical shifts of hydrogen using 1 H-NMR spectroscopy (with hydrogen atom as the hydrogen donor) can effectively study intramolecular hydrogen bonding of salicylic acid conformers [24]. Despite their different mechanisms, both XPS and NMR properties are sensitive to local chemical environment within a molecule. Experimental evidences have revealed that C1s, O1s and N1s CEBEs and C-NMR and H-NMR chemical shifts of molecules, are influenced by molecular structure, chemical bonding, inter-and intra-molecular interactions, isomeric structures and hydrogen bonding . In the present study, experimentally validated quantum mechanical methods are employed, utilizing XPS and NMR techniques, to investigate the C1s CEBE and 13 C-NMR chemical shift of the QC family of strained methano-bridged hydrocarbon derivatives: NBD/QC, NBN, PPL, and NBA, in order to elucidate their unique electronic structures and possible correlations for energy storage.