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n‐Alkanes are widely used in paleoenvironmental reconstructions. However, our understanding of changes in the distribution of n‐alkanes with climatic and environmental factors remains unclear in arid/semi‐arid regions. We sampled 26 surface sediments from three climatic zones across the southwestern Tibetan Plateau to evaluate the sensitivity of chain length distributions of n‐alkanes to climatic and environmental parameters. Our observations demonstrate that average chain length (ACL), proportion of aquatic macrophyte (Paq), carbon preference index (CPI) and ratio of the contents of nC27 and nC31 (nC27/nC31) are all sensitive to hydroclimatic conditions. In contrast to commonly‐adopted assumptions, the correlations between these indices and hydrological parameters are not always good, which indicates that the interpretation of n‐alkane indices is special on the southwestern Tibetan Plateau. These might be related to the vegetation characteristics and seasonality of biological activity, and need to be considered in paleoclimatic reconstruction. The impact of seasonal precipitation on n‐alkanes indices was also evaluated. [ABSTRACT FROM AUTHOR]