Copyright © 2019 American Chemical Society. With the examples of the C K-edge in graphite and the B K-edge in hexagonal boron nitride, we demonstrate the impact of vibrational coupling and lattice distortions on the X-ray absorption near-edge structure (XANES) in two-dimensional layered materials. Theoretical XANES spectra are obtained by solving the Bethe-Salpeter equation of many-body perturbation theory, including excitonic effects through the correlated motion of the core hole and excited electron. We show that accounting for zero-point motion is important for the interpretation and understanding of the measured X-ray absorption fine structure in both materials, in particular for describing the σ∗-peak structure.