We report a systematic experimental study of the mean temperature profile $\theta (\delta z)$ and temperature variance profile $\eta (\delta z)$ across a stable and immiscible liquid–liquid (water–FC770) interface formed in two-layer turbulent Rayleigh–Bénard convection. The measured $\theta (\delta z)$ and $\eta (\delta z)$ as a function of distance $\delta z$ away from the interface for different Rayleigh numbers are found to have the scaling forms $\theta (\delta z/\lambda )$ and $\eta (\delta z/\lambda )$ , respectively, with varying thermal boundary layer (BL) thickness $\lambda$ . By a careful comparison with the simultaneously measured BL profiles near a solid conducting surface, we find that the measured $\theta (\delta z)$ and $\eta (\delta z)$ near the liquid interface can be well described by the BL equations for a solid wall, so long as a thermal slip length $\ell _T$ is introduced to account for the convective heat flux passing through the liquid interface. Direct numerical simulation results further confirm that the turbulent thermal diffusivity $\kappa _t$ near a stable liquid interface has a complete cubic form, $\kappa _t(\xi )/\kappa \sim (\xi +\xi _0)^3$ , where $\kappa$ is the molecular thermal diffusivity of the convecting fluid, $\xi =\delta z/\lambda$ is the normalized distance away from the liquid interface and $\xi _0$ is the normalized slip length associated with $\ell _T$ .