The proton-exchange process is an effective method of fabricating low-loss waveguides based on LiNbO₃ crystals. During proton-exchange, lithium is replaced by hydrogen and Li_1−xH_xNbO₃ is formed. Currently, mechanisms and kinetics of the proton-exchange process are unclear, primarily due to a lack in reliable tracer diffusion data. We studied lithium and hydrogen tracer diffusion in proton-exchanged congruent LiNbO₃ single crystals in the temperature range between 130–230 °C. Proton-exchange was done in benzoic acid with 0, 1, 2, or 3.6 mol% lithium benzoate added, resulting in micrometre thick surface layers where Li is substituted by H with relative fractions between x = 0.45 and 0.85 as determined by Nuclear Reaction Analysis. For the diffusion experiments, ion-beam sputtered isotope enriched ⁶LiNbO₃ was used as a Li tracer source and deuterated benzoic acid as a H tracer source. Isotope depth profile analysis was carried out by secondary ion mass spectrometry. From the experimental results, effective diffusivities governing the lithium/hydrogen exchange as well as individual hydrogen and lithium tracer diffusivities are extracted. All three types of diffusivities can be described by the Arrhenius law with an activation enthalpy of about 1.0–1.2 eV and increase as a function of hydrogen content nearly independent of temperature. The effective diffusivities and the lithium tracer diffusivities are identical within a factor of two to five, while the hydrogen diffusivities are higher by three orders of magnitude. The results show that the diffusion of Li is the rate determining step governing the proton-exchange process. Exponential dependencies between diffusivities and hydrogen concentrations are determined. The observed increase of Li tracer diffusivities and effective diffusivities as a function of hydrogen concentration is attributed to a continuous reduction of the migration enthalpy of diffusion by a maximum factor of about 0.2 eV. Simulations based on the determined diffusivities can reproduce the step-like profile of hydrogen penetration during proton-exchange.