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In this study, we investigate the electronic structure of a spin-triplet superconductor candidate CeRh$_2$As$_2$ using high-resolution angle-resolved photoemission spectroscopy and density functional theory calculations. Notably, Fermi surface nesting hints at connections to magnetic excitation or quadrupole density wave phenomena, elucidating the superconducting mechanisms. Measured band structures reveal primarily localized 4f electrons, with minor itinerant contributions. Additionally, a transition from localized to itinerant behavior and significant c-f hybridization anisotropy underscore the role of f-electrons in shaping electronic properties. These findings deepen our understanding of CeRh$_2$As$_2$'s unconventional superconductivity and magnetism. Further exploration promises advances in superconductivity research.