ZnO is a promising n-type oxide thermoelectric material, which is stable in air at elevated temperatures. In the present study we report the bottom-up approach to create Al-doped ZnO nanocomposites from nanopowders, which are prepared by chemical vapour synthesis. With our synthesis route we are able to create highly doped Al-containing ZnO nanocomposites that exhibit bulk like electrical conductivity. Concurrently, the impact of microstructure of nanocomposites on their thermal conductivity is enormous with a value of 1.0 W/mK for 1%Al-ZnO at room temperature, which is one of the lowest values reported so far on ZnO nanocomposites. The optimization of the Al-doping and microstructure with respect to the transport properties of bulk Al-ZnO nanocomposites leads to a zT value of about 0.24 at 950 K, underlining the potential of our technique.