Isomeric octanols show a variety of dielectric behavior. At low temperatures, some behave as nonpolar liquids, others as polar liquids. This results from the extent of steric hindrance for intermolecular H bonding when the CH3 group is in the proximity of the OH group in the seven-membered -C-C- chain. Differential scanning calorimetric studies of nine isomeric octanols and LiCl solutions of two of them are reported here. These are discussed in terms of structural relaxation, glass transition temperature T-g, configurational contribution to the heat capacity Delta C-p, and distribution of structural relaxation times parameter beta. T-g of the isomers of octanols lies between 148 and 168 K, Delta C-p, between 35 and 82 kJ/mol, and beta between 0.33 and 0.93. Those octanols that behave dielectrically as nonpolar liquids have a broader distribution of relaxation times, or lower beta, than those isomers that behave dielectrically as highly polar liquids. Addition of 5 mol % LiCl increases T-g and Delta C-p, in the former case but decreases both in the latter case, and the distribution of relaxation times broadens in both cases. An analysis in terms of configurational contributions to C-p, shows that steric hindrance of the OH group determines the H-bonded motifs formed in liquid octanols near their glass-liquid transition temperature.