Bitumen, a vital component in road pavement construction, exhibits complex chemo-mechanical properties that necessitate thorough characterization for enhanced understanding and potential modifications. Nuclear Magnetic Resonance (NMR) spectroscopy emerges as a valuable technique for probing the structural and compositional features of bitumen. This review presents an in-depth exploration of the role of NMR spectroscopy in bitumen characterization, highlighting its diverse applications in determining bitumen content, group composition, molecular dynamics, and interaction with additives. Various NMR techniques, including free induction decay (FID), Carr–Purcell–Meilboom–Gill (CPMG), and Pulsed Field Gradient Stimulated Echo (PFGSE), are discussed in the context of their utility in bitumen analysis. Case studies, challenges, and limitations associated with NMR-based bitumen characterization are critically evaluated, offering insights into potential future research directions. Overall, this review provides a comprehensive overview of the current state-of-the-art in NMR-based bitumen characterization and identifies avenues for further advancement in the field.