We measure the hyperfine C-constant of the 3d4s 2 2 D 5/2 atomic state in 45 Sc: C = −0.25(12) kHz. High-precision atomic calculations of the hyperfine structure of the 3d4s 2 2 D 5/2 state and secondorder corrections are performed to infer the nuclear magnetic octupole moment Ω = 1.6(8)µN b. With a single valence proton outside of the doubly-magic calcium core, this element is ideally suited for an in-depth study of the many intriguing nuclear structure phenomena observed within the neighboring isotopes of calcium. We compare Ω to shell-model calculations, and find that they cannot reproduce the experimental value of Ω for 45 Sc. We furthermore explore the use of Density Functional Theory for evaluating Ω, and obtain values in line with the shell-model calculations. This work provides a crucial step in guiding future measurements of this fundamental quantity on radioactive scandium isotopes and will hopefully motivate a renewed experimental and theoretical interest.