Several recent studies found large lithium isotopic fractionations correlated with concentration gradients in pyroxene minerals from lava flows and mantle nodules that were interpreted as indicating diffusion of lithium into the grains. Motivated by these findings experiments were undertaken in which powdered spodumene (LiAlSi2O6) or Li2SiO3 was used to diffuse lithium into Templeton augite or Dekalb diopside grains at 900 °C and oxygen fugacity ranging from log fO2 = −17 to log fO2 = −12. The purpose of these experiments was to determine the diffusion coefficient of lithium in pyroxene minerals and to measure the isotopic fractionation of lithium in the diffusion boundary layer due to the relative mobility of 6Li compared to 7Li. The diffusion profiles of lithium that had not yet reached the center of Templeton augite grains were in most cases sharp steps propagating in from each boundary. In one case a more usual profile with smoothly decreasing lithium concentration with distance from the grain boundary was found. A model in which lithium occupies two different sites – one being fast diffusing interstitial lithium, the other much less mobile lithium in a metal site, reproduced both types of profiles. The step-like profiles arise in the model when interstitial lithium diffusing into the grain is strongly partitioned into abundant metal sites and thus does not penetrate further into the grain until all the metal sites at a given distance become filled. While the rate of propagation of the concentration step can be used to calculate an effective diffusivity for the penetration of lithium into the augite grains, the multiple speciation of lithium precludes making a separate precise determination of the diffusion coefficient of the interstitial lithium. Isotopic fractionations of 7Li/6Li of about 30‰ were found in the step-like diffusion boundary layers, which translate into a ratio of the isotope diffusion coefficients D7 Li/De Li = 0.9592 (i.e., (6/7)β with β = 0.27). The same value of β = 0.27 was also able to fit the isotopic fractionation data from the experiment with the smoothly decreasing lithium concentration profile. The laboratory experiments confirmed that diffusion of lithium produces large kinetic isotopic fractionations and thus highlight the importance of isotopic measurements for discriminating when a particular instance of chemical zoning in minerals was the result of diffusion or some other process such crystal growth from an evolving melt. The experiments also showed that, contrary to conventional wisdom, isotopic gradients do not dissipate faster than gradients in the parent element, indeed the contrary is seen in several of the Templeton experiments where very large lithium isotopic fractionations persisted after the lithium concentration had become effectively homogenized. Published data of lithium isotopic fractionation of zoned augite grains from a Martian meteorite and in clinopyroxene grains from both lava flows on the Solomon Islands and from a San Carlos mantle xenolith were modeled in terms of lithium diffusion with an isotope fractionation parameter β between 0.25 and 0.30, which is very similar to that derived from the laboratory experiments.