Covalent bonding between transition metal atoms is a common phenomenon in honeycomb lattices of layered materials, which strongly affects their electronic and magnetic properties. This work presents a detailed spectroscopic study of α-MoCl₃, 2D van der Waals material with covalently bonded Mo₂ dimers, with a particular focus on the Mo-Mo bonding. Raman spectra of α-MoCl₃ were studied with multiple excitation laser lines chosen in different parts of the absorption spectrum, while polarization measurements aided in the symmetry assignment of the observed modes. Furthermore, far-IR measurements and (Density Functional Theory) DFT phonon computations were performed to complete vibrational assignment. Polarized absorption, PL, and photoelectron spectroscopy supported by DFT calculations were employed to understand the consequences of the Mo-Mo bonding for the electronic structure and the localization/delocalization balance in d³-d³ interactions. A coupling of dimerization-related structural and electronic properties was revealed in the strong resonance Raman enhancement of the Mo-Mo stretching mode at 153 cm⁻¹ when the excitation laser matched the electronic transition between σ-bonding and antibonding orbitals of the Mo₂ dimer (σ → σ*). The deeper understanding of the metal-metal bonding and identification of the vibrational and electronic spectroscopic signatures of the dimerization will be of great use for the studies of electron delocalization in magnetic van der Waals materials.