Hybrid strategy of ZnO with carbon nanotube (CNT) has been attempted, and synergistic effects have been demonstrated in ZnO-CNT hybrid nanostructures owing to the advantageous effects of interface modification on the charge transport process. Here, we report the effects of interface control using multiwall CNTs (MWCNTs) on the charge transport properties in Al-doped ZnO (AZO) nanocomposite. Although the AZO-MWCNT nanocomposite is composed of numerous nanograins, it shows single crystalline charge transport behavior due to significantly weakened grain-boundary scattering at room temperature. The dominant charge transport mechanism is converted from lattice vibration scattering to grain-boundary scattering at 873 K due to the variation in the charge distribution at the grain boundary. The results demonstrate that interface control using carbon nanomaterials has a significant effect on the charge transport behavior in AZO nanocomposite.