Polycrystalline thick film of zinc oxide (ZnO) is grown on a unique silicon substrate with a hierarchical structure,silicon nanoporous pillar array (Si-NPA), by using a vapour phase transport method. It is found that as-grown ZnO film is composed of closely packed ZnO crystallites with an average size of ～10 μm. The film resistivity of ZnO/Siheterostructure is measured. Theoretical analysis shows that the carrier transport across ZnO/Si-NPA heterojunction is dominated by two mechanisms, i.e. a thermionic process at high voltages and a quantum tunnelling process at low voltages.