Volcanic tuffs are important in determining the stratigraphic age of sedimentary sequences, which is closely related to the tectonic, sedimentological, geomorphological, palaeoclimatic, and palaeo-ecological evolution of the sequences. However, it may be difficult practically to identify tuffs in stratigraphic sections, especially when they are altered after deposition. In this study, a series of petrographic, mineralogical, and geochemical analyses was deployed in the tuff layers cropping out in the Lunpola Basin of the central Tibetan Plateau, which is a crucial site for studying the dynamics and processes of the Cenozoic uplift of the Tibetan Plateau and its environmental impacts. In these pyroclastic layers, authigenic analcime is the main volcanic glass alteration product. The analcime-bearing samples are Na-enriched, in contrast to the K-abundant magmatic rocks in the central Tibetan Plateau. The distribution patterns of the rare earth elements (REEs) of the bulk analcime-bearing samples are similar to those of the magmatic rocks but different from those of the analcime-poor sediments and analogues of well-mixed upper continental material (e.g. the upper continental crust and post-Archaean Australian average shales). The distinct distributions of Na and REEs among analcime-bearing samples, analcime-poor sediments, and volcanic rocks reveal that analcime formed both from alteration of volcanic material and from mixing processes with non-volcanic sediments. It is proposed, therefore, that the discrimination plot of Na2O/Al2O3-(La/Yb)N may be used to distinguish the analcime-related pyroclastic rocks from the basin sedimentary sequence, and thus it may provide a means of discriminating between various volcanic material and of supporting age dating by tephrochronology in the central Tibetan Plateau.