The research successfully revealed the fabrication of zinc oxide (ZnO) nanofilms with hexagonal (002) structure grown on porous silicon (PS) substrate using chemical bath deposition method. Their structural, optical, and electric characteristics were investigated through X-ray diffraction, field emission scanning electron microscopy (FESEM), and photoluminescence spectroscopy. FESEM showed that ZnO nanofilms were formed on top and inside the pores of PS substrate with hexagonal shape. The strong ultraviolet emission of ZnO nanofilms is also presented at ∼383 nm near the band edge energy levels which can be applied in semiconductor device both photoelectron devices and chemical sensors. In addition, current-voltage (I-V) characteristics revealed that the current level for ZnO nanofilms was about three times larger than for PS layer.