There is clear evidence that rapid warming has been fuelling significant changes in the ocean and cryosphere in the Antarctic Peninsula region. Less is known about how terrestrial biological ecosystems, particularly plants, are responding to warming and hydroclimatic change. We show that high evaporative environmental conditions and microclimate associated with topography lead to humidity-dependent evaporative effects on the oxygen isotope ratios (δ18O) of moss waters and α-cellulose in the northern Antarctic Peninsula, based on a spatial (> 400 km) isotopic survey at 14 sites over 24 days during summer 2020. The δ18O of moss waters define a water line of δ2H = 4 × δ18O + 37 for Polytrichum strictum and δ2H = 3.8 × δ18O + 38.9 for Chorisodontium aciphyllum, indicating enrichment compared to line slopes ranging from 6.7 to 8.5 for snow, standing water, previous published snapshots of moss waters and the long-term local meteoric water lines along the Antarctic Peninsula. The δ18O of moss waters negatively correlated with relative humidity (which ranged from ~50% to 100%) and not with temperature or latitude, where a higher δ18O indicates increased evaporative enrichment or dry conditions. A positive correlation between the δ18O of moss waters and α-cellulose (ρ = 0.397, P = 0.011) for P. strictum (ρ = 0.533, P = 0.007) but not C. aciphyllum suggests that the high evaporative conditions from the season imprinted on the cellulose. Lastly, we found significant positive correlations between topographic aspect (north-exposedness) and the δ18O of moss waters (ρ = 0.569, P < 0.001) and α-cellulose (ρ = 0.579, P < 0.001), indicating that irradiance on north-facing slopes promotes drier conditions and evaporative enrichment. Topographic aspect (and resulting microclimate) is an important and predictable determinant of the δ18O of moss waters and α-cellulose. This study highlights that mosses are sensitive recorders of climatic and non-climatic conditions in polar terrestrial ecosystems.