Precipitation and catchment characteristics of mountainous headwaters can vary largely within short distances. It remains unclear how these two factors determine the contribution of event water and pre-event water to stormflow. We investigated this in five neighboring headwaters with high annual precipitation amounts (>2,000 mm y⁻¹) in a steep pre-alpine region in Switzerland. Rainfall and streamwater of 13 different rainstorms were sampled (P: 5 mm intervals, Q: 12 to 51 samples per events) to perform a two-component isotope hydrograph separation. Pre-event water contributions based on δ¹⁸O or δ²H computation were similar. The pre-event water contributions of headwaters depended largely on rainfall (amount and intensity) and varied more between events than between catchments, despite clear differences in land cover between the catchments. Furthermore, antecedent wetness was not found to control pre-event water contribution. With increasing rainfall amount, the proportion of rainfall in runoff increased and changed from pre-event to event water dominated. The variable rainfall amount and small active storage (organic soil horizon, 20–50 cm) resulted in a threshold in the upper soil horizon with subsequently more variable pre-event water contribution. Our results show the necessity of sampling in different headwaters and events to better understand controlling factors in runoff generation.