Quasi-aligned porous ZnO nanowire arrays are promising architectures for potential applications in catalysts, gas sensors and solar cells. However, processes for conversion of ZnO nanowire arrays into porous ones have rarely been reported. Here, we report a facile chemical method for the synthesis of ZnO nanowire array with porous surface. The morphology and structure of the obtained products have been investigated with field-emission scanning electron microscopy and high-resolution transmission electron microscopy. Time-dependent experiments have also been carried out to better understand the formation process of porous structures on the nanowire surfaces. The obtained porous ZnO nanowire arrays may find potential applications in catalysts, solar cells and gas sensors due to the large surface area of the yielded products.