The Dolná Ves K-bentonite deposit is one of a few known economic accumulations of illite-smectite in the world. Several studies have been done on the illite-smectitic component isolated from the Dolná Ves K-bentonite, but there is a shortage of analytical data on the K-bentonite itself. The main goal of the present study was to perform mineralogical and physico-chemical characterizations of various technological types of K-bentonites from the Dolná Ves deposit to better understand the relationships between the various qualitative types and their properties. The type I (high-grade) K-bentonite contains 88–91 wt.% of illite-smectite. The type II (low-grade) K-bentonite contained substantially less illite-smectite, ranging from 37 to 63 wt.%. The illite-smectites isolated from the type I K-bentonites displayed greater expandability, contained more octahedral Mg and less octahedral Fe, had greater cation exchange capacity (CEC), smaller thickness of fundamental particles, and thinner illite-smectite crystals in comparison with illite-smectites from the type II K-bentonites. The LOI (loss-on-ignition) and Al2O3 content increased with increasing amount of illite-smectite. The increase in the expandability by 10% corresponded to an increase in CEC by ~10 meq/100 g. The type I K-bentonites had much greater mass loss at <250°C due to greater expandability. The best tilemaking performance was expected for the type I K-bentonite. This raw material could also be potentially valuable for the pharmaceutical, cosmetic and food industries. Overall, the results showed that the studied technological types of K-bentonites from the Dolná Ves deposit differ not only in terms of illite-smectite contents but also in terms of the nature of the illite-smectites.