We present a comprehensive experimental and theoretical characterization of the electronic structure of four 1,1-diaryl-2,3,4,5-tetraphenylsiloles (aryl = phenyl, 2-(9,9-dimethylfluorenyl), 2-thienyl, pentafluorophenyl). Solid-state electron affinities and ionization potentials of these siloles were measured using inverse-photoelectron spectroscopy (IPES) and photoelectron spectroscopy (PES), respectively; the density of electronic states obtained from calculations performed at the density functional theory (DFT) level corresponds very well to the PES and IPES data. The direct IPES measurements of electron affinity were then used to assess alternative estimates based on electrochemical and/or optical data. We also used DFT to calculate the reorganization energies for the electron-transfer reactions between these siloles and their radical anions. Additionally, optical data and ionization potential and electron affinity data were utilized to estimate the binding energies of excitons in these siloles.