The self-diffusion of lithium in congruent LiNbO3 single crystals was investigated at low temperatures between 379 and 523 K by neutron reflectometry. From measurements on 6LiNbO3 (amorphous film)/natLiNbO3 (single crystal) samples, Li self-diffusivities were determined in single crystals down to extremely low values of 1 × 10−25 m2 s−1 on small length scales of 1–10 nm. The measured diffusivities are in excellent agreement with (extrapolated) literature data obtained by experiments based on Secondary Ion Mass Spectrometry and Impedance Spectroscopy. The tracer diffusivities can be described by a single Arrhenius line over ten orders of magnitude with an activation enthalpy of 1.33 eV, which corresponds to the migration energy of a single Li vacancy. A deviation from the Arrhenius behaviour at low temperatures, e.g., due to defect cluster formation is not observed.