We describe an innovative interfacial design concept and nanostructuring of novel BixSb2-xTe3 (BST) nanoassembled films comprising unique air-solid interfaces from micro-scaled open gaps to isolated sealed mesopores, and high-quality solid-solid ones including the coherent grain boundaries and specific twins, utilizing pulsed laser deposition (PLD), for potentially activating multiple thermoelectric enhancing mechanisms. The unusual mesopore embedded BST films exhibit the highest power factor of ∼33 μW cm-1 K-2, which is comparable to or higher than the previously reported values for BST, and the corresponding relatively low thermal diffusivity in contrast to that for dense pore-less BST films evidently reveals the crucial role of the three-dimensionally and densely arranged air-solid interfaces in significantly arising the phonon scattering.