Two different clusters that have the topology of chabazite but different shapes have been used as a model for the Brønsted sites in chabazite. One of the clusters consists of eight tetrahedral atoms (8T) arranged in a ring and the other represents an intersection of two 8T rings. The adsorption of water and methanol on the two stable proton positions in chabazite has been studied using the B3LYP functional. The coordination of water and methanol with respect to the zeolite fragments were found to be similar, but with methanol situated closer to the acid site than water. The anharmonic zeolite OH stretch frequencies were found to be in the range of 2170–2500 cm−1 and 1457–2074 cm−1 in the presence of water and methanol, respectively. As a measure of the acidity of the bridging hydroxyl groups in chabazite the shift of the zeolite OH stretch frequency upon adsorption has been used. We have found that the proton attached to the oxygen atom O1 to be more acidic than the proton attached to the oxygen atom O3. Also, in the closed ring clusters the zeolite hydroxyl groups are more acidic than in the open clusters. This is not due to a steric effect as the orientation of the adsorbates with respect to the zeolite site is very similar for both clusters. The anharmonicities of the zeolite O–H bond account for about 40% in the redshift upon the adsorption of water or methanol.