The densities and viscosities of binary mixtures of cyclohexane + picoline have been measured at 298.15 and 313.15 K over the whole composition range. From these, excess volumes V(E), excess viscosities eta(E) and excess energies of activation for viscous flow G*E have been calculated. V(E) is positive and both eta(E) and G*E are negative. These results are consistent with the self-association of picolines and the non-polar character of cyclohexane, which produces the dissociation of the picolines.