The localized model of a chemical bond has had a long and prominent role in chemistry, but situations of extended charge delocalization and dipole effects remain topics in need of greater understanding. Both orbital delocalization in isolated molecules and induced molecular dipoles in condensed phases serve to move electron density and influence the chemical and physical properties of a system. This dissertation studies these aspects of electronic structure for selected organic, inorganic, and organometallic systems by means of electronic structure calculations and photoelectron spectroscopy, which is well-suited for studying both intramolecular and intermolecular effects by providing a direct probe of orbital energies and characters. Photoelectron spectra of P₄ and AsP₃ reveal differences in the molecular symmetry and cationic state effects between the two molecules in Chapter 3. Despite these differences, AsP₃ is found to have electron delocalization and vibrational structures that are comparable to P₄. A similar study of the delocalized -system of 2H-1,2,3-triazole in Chapter 4 relates the vibrational structure in photoelectron spectroscopy data to a series of Rydberg excitations in the vacuum UV photoabsorption spectrum. Chapters 5 and 6 examine extended electronic structures in organometallic complexes. The electron delocalization and charge transfer between two Ru centers along a bridging ethynediyl ligand is studied in [CpRu(CO)₂]₂(μC≡C). Details of the Ru-alkynyl interaction were explored by comparing the spectra of CpRu(CO)₂C≡CMe with CpRu(CO)₂Cl, including the -backbonding ability of alkynyl ligands. Chapter 6 moves from the realm of intramolecular effects to intermolecular interactions to understand how surrounding media affect electronic properties of molecules. The reversal of ionization energies between the gas and solid phases of M(CO)₄dmpe and M(CO)₄dppe, where M = Mo, W, is explored with photoelectron spectroscopy. The surrounding molecular environment stabilizes the cation, resulting in this reversal that extends to core ionization energies. The variety of systems presented illustrates the wide applicability of photoelectron spectroscopy and computations to different electronic structure studies, including how gas phase results can be related to condensed phase studies. This work continues the progress of photoelectron spectroscopy from small molecules to larger molecular systems and even further to bulk systems.