Human-induced (i.e., secondary) salinization affects aquatic biodiversity and ecosystem functioning worldwide. While agriculture or resource extraction are the main drivers of secondary salinization in arid and semi-arid regions of the world, the application of deicing road salt in winter can be an important source of salts entering freshwaters in cold regions. Alpine rivers are probably affected by salinization, especially in highly populated mountain regions, although this remains to be explored. In this study, we analyzed multi-year conductance time series from four rivers in the European Alps and demonstrated that the application of deicing road salt is linked to peaking rivers’ salinity levels during late winter/early spring. Especially in small catchments with more urban surfaces close to the rivers, conductance increased during constant low-flow periods in late winter and was less correlated with discharge than in summer. Thus, our results suggest that small rivers highly connected to urban infrastructures are prone to considerable salinity peaks during late winter/early spring. Given the low natural level of salinities in Alpine rivers, the aquatic biodiversity might be significantly affected by the recorded changes in conductance, with potential consequences on ecosystem functioning. Thereby, we urge the research community to assess the impact of secondary salinization in Alpine rivers and call for an implementation of management practices to prevent the degradation of these pristine and valuable ecosystems.