Background, aim, and scope Since weathering processes constrain the cycle of elements and their transportation from the continents to the lake/ocean reservoirs, shape the topography of continents, and regulate global carbon cycle and therefore climate changes by consuming atmospheric carbon dioxide over geological time-scales, how to effectively trace continental weathering processes is one of key scientific topics of supergene geochemistry. Being one of the most promising silicate-weathering tracers, lithium (Li) isotopes have long been exploded to trace continental weathering and thus to reconstruct secular weathering scenarios. To acquire effective research methodology, review of establishing Li isotopes to be a silicate-weathering tracer is thus essential. Materials and methods This paper reviewed current major developments, problems and challenges of using Li isotopes to trace weathering with respects to its major reservoirs, weathered crust, riverine systems, leaching experiments, and modeling simulation which have progressively developed in the past decades. Results Owing to large mass difference between ~6Li and ~7Li, one valence, and no effect of redox conditions and living beings, if not all, at least at catchment scale, Li isotopes own potential to trace continental weathering processes. However, its sources and controlling factors of Li fractionation during weathering processes are controversial. Discussion Changes in Li isotopic compositions from weathered crust to fresh bedrocks are complex and even reverse, whereas controlling factors for Li isotopic variations in riverine system are various and controversial, in particular for large river systems. Leaching experiments and modeling simulation for Li isotopic compositions are at an early stage. More attentions are focused on seasonal variation in riverine Li isotopic compositions at small, monolithological catchment. Conclusions We pointed out that Li isotope system does have its potential and uniqueness in tracing continental weathering, especially for silicate weathering. Recommendations and perspectives In order to reduce the uncertainty of tracing silicate weathering processes using Li isotopes, elaborating leaching experiments of rocks/minerals, marrying large and small catchments, enhancing computation simulation, and coupling of multi-isotopes are suggested to be needed in future.