Apparent molar heat capacities, C_m^app, at dilute alcohol concentrations and excess molar heat capacities, C_p^E throughout the concentration range were determined at 25°C for the following systems: methanol, ethanol, propan-1-ol, hexan-1-ol and decan-1-ol mixed with n-octane, oct-1-ene and oct-1-yne; in addition, the following mixtures were also measured: hexan-1-ol with oct-4-yne, cyclohexane, cyclohexene, benzene, hex-1-ene, dec-1-ene and an equimolar mixture of n-octane+oct-1-yne. The experimental C_m^app show a maximum against alcohol concentration; this maximum is reduced in magnitude and displaced to higher alcohol concentrations when the inert n-octane is substituted by the unsaturated oct-1-ene, oct-1-yne, oct-4-yne, cyclohexene or benzene which act as weak proton acceptors, forming complexes or cross-associated species with the alcohol molecules. The present data clearly indicate that there are alcohol–alkene complexes in solution, which are weaker than the alcohol–alkyne ones, but detectable through heat capacity measurements. The C_m^app data for alkan-1-ols when plotted against ψ₁, the concentration of hydroxyl groups in the mixture, follow a single corresponding states curve for each of the solvents. For all alkan-1-ols, C_p^E display the following behaviour: C_p^E (oct-1-yne)<C_p^E (oct-1-ene)<C_p^E (n-octane) at low alcohol concentrations and C_p^E (oct-1-yne)>C_p^E (oct-1-ene)>C_p^E (n-octane) at higher alcohol concentrations, the cross-over point being between 0.1 and 0.2 alcohol mole fraction. To interpret the data, the Treszcanowicz–Kehiaian (TK) model for associated liquids has been used. The parameters of the model, i.e. volumetric equilibrium constants and enthalpies of formation for alcohol–unsaturated hydrocarbon 1:1 complexes have been fitted to the dilute alcohol data. With these parameters, the TK model is able to give correct qualitative predictions of the C_p^E results throughout the concentration range. Using the Flory lattice model, the volumetric equilibrium constants were transformed into a unique or intrinsic equilibrium constant, which is independent of molecular size and describes the alcohol–alkene and alcohol–alkyne association. A detailed analysis of the data for hexan-1-ol+oct-1-yne and hexan-1-ol+oct-4-yne indicates that the dominating interaction in the formation of the alcohol–unsaturated hydrocarbon complex is that occurring between the proton of the hydroxy group of the alcohol and the negative electron density in the double or triple bond, producing what can be termed a H-bond. Using the parameters obtained when analyzing excess volumes V^E and excess enthalpies H^E for similar and common systems (T. M. Letcher etal., FluidPhaseEquilib., 1995, 112, 131), the ERAS model was used to predict C_p^E, finding that it is unable to give a satisfactory rendering of the present heat capacity data.