ABSTRACT:11 This paper reports the cross-plane thermal conductivity of highly ordered amorphous and crystalline templated mesoporous titania 12 thin films measured by the 3ω method from 30 to 320 K. Both solÀgel and nanocrystal-based films were synthesized by evaporation-13 induced self-assembly, with average porosity of 30% and 35%, respectively. The pore diameter ranged from 14 to 25 nm. The size of 14 crystalline domains in polycrystalline mesoporous films were 12À13 nm, while the nanocrystals in the nanocrystal-based film were 15 9 nm in diameter. At high temperatures, the thermal conductivity of amorphous dense and mesoporous films showed similar trends 16 with respect to temperature. This was attributed to the fact that the presence of pores had a purely geometrical effect by reducing the 17 cross-sectional area through which heat can diffuse. By contrast, the thermal conductivity of polycrystalline dense and mesoporous 18 films behaves differently with temperature due to phonon scattering by pores and crystalline nanosize domains. In addition, at low 19 temperatures, the presence of pores caused the thermal conductivity of mesoporous films to be less temperature dependent than 20 their dense counterparts. Despite its crystallinity, the thermal conductivity of the nanocrystal-based film was about 40% less than that 21 of the polycrystalline mesoporous films. This was mainly attributed to its larger porosity, smaller crystal size, and strong phonon 22 scattering at the poorly interconnected nanocrystal boundaries. These results suggest various ways to control the thermal 23 conductivity of mesoporous materials for various applications.