The hydrogen isotopic composition of leaf wax–derived n-alkane (δ²H_n-alkane) and oxygen isotopic composition of hemicellulose–derived sugar (δ¹⁸O_sugar) biomarkers are valuable proxies for paleoclimate reconstructions. Here, we present a calibration study along the Bale Mountains in Ethiopia to evaluate how accurately and precisely the isotopic composition of precipitation is imprinted in these biomarkers. n-Alkanes and sugars were extracted from the leaf and topsoil samples and compound–specific δ²H_n-alkane and δ¹⁸O_sugar values were measured using a gas chromatograph–thermal conversion–isotope ratio mass spectrometer (GC–TC–IRMS). The weighted mean δ²H_n-alkane and δ¹⁸O_sugar values range from − 186 to − 89‰ and from + 27 to + 46‰, respectively. Degradation and root inputs did not appear to alter the isotopic composition of the biomarkers in the soil samples analyzed. Yet, the δ²H_n-alkane values show a statistically significant species dependence and δ¹⁸O_sugar yielded the same species–dependent trends. The reconstructed leaf water of Erica arborea and Erica trimera is ²H– and ¹⁸O–enriched by + 55 ± 5 and + 9 ± 1‰, respectively, compared to precipitation. By contrast, Festuca abyssinica reveals the most negative δ²H_n-alkane and least positive δ¹⁸O_sugar values. This can be attributed to “signal–dampening” caused by basal grass leaf growth. The intermediate values for Alchemilla haumannii and Helichrysum splendidum can be likely explained with plant physiological differences or microclimatic conditions affecting relative humidity (RH) and thus RH–dependent leaf water isotope enrichment. While the actual RH values range from 69 to 82% (x̄ = 80 ± 3.4%), the reconstructed RH values based on a recently suggested coupled δ²H_n-alkane –δ¹⁸O_sugar (paleo–) hygrometer approach yielded a mean of 78 ± 21%. Our findings corroborate (i) that vegetation changes, particularly in terms of grass versus non–grassy vegetation, need to be considered in paleoclimate studies based on δ²H_n-alkane and δ¹⁸O_sugar records and (ii) that the coupled δ²H_n-alkane –δ¹⁸O_sugar (paleo–) hygrometer approach holds great potential for deriving additional paleoclimatic information compared to single isotope approaches.