Nuclear magnetic resonance (NMR) spectroscopy is a versatile tool for investigating various physicochemical properties of biomolecules. Among diverse applications of biomolecular NMR spectroscopy, ¹⁹F-based methodology has recently attracted much attention from researchers in protein science owing to its advantageous applicability to proteins of high molecular weights or heterogeneous structural states. In this mini-review, the recent application example of ¹⁹F NMR to transthyretin, a representative amyloidogenic protein, thus being an important yet challenging target for structural investigation, is summarized along with some perspectives for its future directions.