Catalyst- and seed layer-free zinc oxide (ZnO) thin films were grown on porous silicon (PS) by a hydrothermal method. Atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and photoluminescence (PL) were carried out to investigate the structural and optical properties of the PS and the ZnO thin films. The ZnO thin films have an extraordinary tendency to grow along the a-axis with a hexagonal wurtzite structure. The growth rate of the ZnO thin films was increased with the increase in the precursor concentration. The crystal quality of the ZnO thin films was improved, and the residual stress was decreased as their thickness increased. Monochromatic indigo and red light emission peaks were observed from the ZnO thin films and the PS, respectively. At an excessively high precursor concentration, a green light emission peak was also observed in the ZnO thin films. The luminescent efficiency of the indigo light emission peak was enhanced with the increase in the precursor concentration.