Nanowires have recently attracted more attention because of their low-dimensional structure, tunable optical and electrical properties for next-generation nanoscale optoelectronic devices. CdS nanowire array, which is (002)-orientation growth and approximately perpendicular to Cd foil substrate, has been fabricated by the solvothermal method. In the temperature-dependent photoluminescence, from short wavelength to long wavelength, four peaks can be ascribed to the emissions from the bandgap, the transition from the holes being bound to the donors or the electrons being bound to the acceptors, the transition from Cd interstitials to Cd vacancies, and the transition from S vacancies to the valence band, respectively. In the photoluminescence of 10 K, the emission originated from the bandgap appears in the form of multiple peaks. Two stronger peaks and five weaker peaks can be observed. The energy differences of the adjacent peaks are close to 38 meV, which is ascribed to the LO phonon energy of CdS. For the multiple peaks of bandgap emission, from low energy to high energy, the first, second, and third peaks are contributed to the third-order, second-order, and first-order phonon replica of the free exciton A, respectively;the fourth peak is originated from the free exciton A;the fifth peak is contributed to the first-order phonon replica of the excitons bound to neutral donors;the sixth and seventh peaks are originated from the excitons bound to neutral donors and the light polarization parallel to the c axis of hexagonal CdS, respectively.