AbstractThe measurement of isotopic ratios provides a privileged insight both into nucleosynthesis and into the mechanisms operating in stellar envelopes, such as gravitational settling. In this article, we give a few examples of how isotopic ratios can be determined from high‐resolution, high‐quality stellar spectra. We consider examples of the lightest elements, H and He, for which the isotopic shifts are very large and easily measurable, and examples of heavier elements for which the determination of isotopic ratios is more difficult. The presence of 6Li in the stellar atmospheres causes a subtle extra depression in the red wing of the 7Li 670.7 nm doublet which can only be detected in spectra of the highest quality. But even with the best spectra, the derived 6Li abundance can only be as good as the synthetic spectra used for their interpretation. It is now known that 3D non‐LTE modelling of the lithium spectral line profiles is necessary to account properly for the intrinsic line asymmetry, which is produced by convective flows in the atmospheres of cool stars, and can mimic the presence of 6Li. We also discuss briefly the case of the carbon isotopic ratio in metal‐poor stars, and provide a new determination of the nickel isotopic ratios in the solar atmosphere. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)