By the unique method of polymer solution self-assembling and its complex effect, zinc oxide (ZnO) nanowires were fabricated on the Si substrate pretreated with a method of electroless plating. The sample composition and surface morphology were observed and characterized by field emission scanning electron microscope (FE-SEM) and energy dispersive X-ray spectrometry (EDS). It was found that the size of diameter mostly was 50 nm, and the lengths reached several microns; the sample was basically composed of elements Zn and O, and the ratio of Zn/O was about 1 : 1. By the comparison of different morphology, UV absorption and PL spectra of the samples with electroless plating and without electroless plating, it was found that the electroless plating was a more effective method for controlling the length and diameter size of the nanowires, and there was a strong near UV emission peak at about 385 nm, which results from the exciton composite and collision. Furthermore, the UV absorption and PL spectra of the samples were analyzed at different pH value and reaction time. The growth process and mechanism of the ZnO nanowires were discussed, and it was considered that the growth process was controlled by the effects of catalyzed active particles via electroless Ni plating and the complex function of the polymer network.