Tetraphenyl ammonium (Ph4N+ ) has long been considered a phantom ion due to the difficulty in synthesizing aryl ammonium compounds. Following the successful synthesis of Ph4N+ last year (2022), the equilibrium geometries of Ph4X (X = B-, Al-, and Ga- of group 13; C, Si, and Ge of group 14; and P+ and As+ of group 15) have been optimized using the B3LYP/6-31G(d,p) method with no symmetry constraints. According to the optimized structural data, Ph4N+ is considered the most sterically hindered molecule in this series of compounds, which reflects the difficulty of its synthesis. The calculated total energies of the Ph4X compounds reveal that their energies decrease down the group, and the cationic forms (group 15) are less energetic than their neutral (group 14) and anionic (group 13) counterparts. The optimized geometrical parameters were used to compute the UV–vis, IR, 1H NMR, and 13C NMR spectra of the nine terephenyl compounds. The frontier molecular orbital energies were used to determine ionization potentials, electron affinity, and other global reactivity descriptors of the nine Ph4X compounds. An accurate assignment of vibrational bands was made using the potential energy distribution (PED) method. The B3LYP/6-31G(d,p) method yielded good agreement with available experimental data for the molecules. The low HOMO-LUMO gaps suggest potential nonlinear optical properties of these compounds.