Understanding the nature of selenium centred hydrogen bond is a growing field of research. Intermolecular C-H···Se hydrogen bond has not yet been investigated experimentally in aromatic molecules. The current work aims at understanding the nature and origin of C-H···Se hydrogen bond interaction between phenylacetylene (C₈H₆) and dimethyl selenide (Se(CH3)₂). The 1:1 complex of [C₈H₆-Se(CH3)₂] is formed in nitrogen matrix at 14 K and probed using infrared spectroscopy. The experimentally obtained infrared spectra have been corroborated with simulated spectra. The nature of the complex has been delineated using Atoms in Molecules (AIM) theory, Natural Bond Orbital (NBO) analysis, and energy decomposition analysis by Symmetry Adapted Perturbation Theory (SAPT).