X-ray Absorption Near-Edge Spectroscopy (XANES) has emerged as a potent tool for delving into the local electronic and structural properties of catalyst molecules and materials. In catalysis, the ability to unravel the chemical environment of the active site at the atomic level is pivotal in understanding the reaction mechanisms and advancing catalytic processes. XANES contain valuable information about the oxidation state, coordination environment, and the local symmetry of the metal centers in the catalysts, offering a unique perspective on their reactivity and selectivity. In particular, in the K-edge XANES of 3d transition metals-based catalysts, the rising edge manifests 1s → 4p transition that is used to estimate the charge on the metal center, metal-ligand overlap via shakedown transitions and geometric structure. However, various factors, such as spin-state, multiple scattering, metal-ligand distances, etc. influence the position of the rising edge. The pre-edge region that emerges as the result of electric-dipole forbidden but quadrupole-allowed 1s → 3d transition, offers a distinctive means to investigate the electronic and geometric structure, such as 3d vacant orbitals and thus, the spin-state and the oxidation state of the metal centers. On the contrary, the intensity of the pre-edge bands increases when a decrease in centrosymmetry of the molecule facilitates the mixing of metal p character into molecular d-orbitals. However, the subtle features obtained in the XANES spectra like the metal-hydride formation and second-shell coordination are difficult to rationalize based on solely the experimental XANES. Therefore, through computational simulation of XANES spectra coupled with molecular orbital analysis, a more in-depth understanding of the underlying electronic interactions between the metal center and its coordination environment can be obtained. The integration of computational and experimental XANES proves to be a resilient approach, providing a detailed analysis that facilitates a thorough characterization of structural features of a material.