By applying a model of a randomly mixed packing of spheres of two sizes to binary liquid mixtures, the thermal conductivity of the mixture is related to the physical properties of each component through the number of contact points. Further, two parameters are introduced to account for the effect of the hydrogen bond and are correlated with the Lennard‐Jones (6‐12) parameters σ and ϵ, or the boiling temperature. In comparing the calculated values with the experimental data for 13 aqueous liquids and 21 non‐aqueous liquid systems, the present equation turns out to be more accurate than previous ones.