Enthalpies of mixing HMmhave measured for binary mixtures of tetrachloroethylene with six alkan–1–ols (propan–1–ol, butan-1–ol, pentan–1–ol, hexan–1–ol, heptan–l–ol and octan–l–ol) at 298.15 K using a Parr 1451 solution calorimeter. All the studied mixtures present exothermic event and showed minimum negative HMmvalues in mixtures from propan–1–ol to octan–1–ol in mixtures rich in tetrachloroethylene region around 0.65–0.70 mole fraction. The mixing HMmvalues increases with the chain length of alkan–1–ols. The experimental data explained in term of dissociation of self–associated alkan–1–mols and tetrachloroethylene.