Textural and compositional variations of Na-bentonites from the Pellegrini Lake deposit (Neuquén Basin) have been established, with special emphasis on petrographic features in order to better understand the genetic pathways in their formation. In this region, two bentonite beds named “white bentonite” and “green bentonite” are mined mainly for the oil and foundry industries. The genesis of these beds was studied using petrological (petrography, SEM and TEM), mineralogical (DRX, FT-IR, DTA-TGA, 27Al MAS NMR) and geochemical (ICP-AES) data from two quarries named COR and CA. The bentonites mainly consist of Na-montmorillonite, with lesser amounts of quartz, plagioclase, potassium feldspar, illite, zeolite, barite and gypsum. Mineralogical and petrographical evidence indicates that the authigenic smectite was formed by devitrification of unstable glass shards in a shallow coastal marine environment. Green bentonite would be the result of several episodes of volcanic ash-fall input from multiple eruptions with a higher degree of alteration uppermost in the bed. In this case, the alteration would have occurred in a reducing environment as evidenced by the greenish colouration of these bentonites, the Ce anomaly and the presence of pyrite. Meanwhile, white bentonite would have formed in a less restricted environment than green bentonite, as evidenced by the existence of intercalations of silt-sized grains and a higher amount of detrital grains in the clay groundmass transported probably by fresher waters. The presence of celestine, barite, halite and gypsum indicates evaporitic conditions after smectite formation. The observed secondary gypsum and iron staining of surfaces are much later processes. Green bentonite samples indicate a trachyandesite composition of the parent material, while the white bentonite suggests a parent material most related to a rhyodacite/dacite composition showing that the characteristics of the volcanism might have changed with time.