Bentonite is one of the most widespread used clays connected with various applications. In the case of foundry technology, bentonite is primarily used as a binder for mold manufacture. Thermal stability of bentonites is a natural property of clay minerals and it depends on the genesis, source and chemical composition of the clay. This property is also closely connected to bentonite structure. According to DTA analysis if only one peak of dehydroxylation is observed (about 600 oC), thecis- isomerism of bentonite is expected, while two peaks of de-hydroxylation (about 550 and 850 oC) are expected in thetrans- one. In this overview, the bentonite structure, the water - bentonite interaction and the sweling behavior of bentonite in connection with the general technological properties of bentonite molding mixture are summarized. Further, various types of methods for determination of bentonite thermostability are discussed, including instrumental analytical methods as wel as methods that employ evaluation of various technological properties of bentonite binders and/or bentonite molding mixtures.