In this study, nanocolumnar zinc oxide thin films were catalyst-free electrodeposited directly on n-Si and p-Si substrates, what makes an important junction for optoelectronic devices. We demonstrate that ZnO thin films can be grown on Si at low cathodic potential by electrochemical synthesis. The scanning electron microscopy SEM showed that the ZnO thin films consist of nanocolumns with radius of about 150 nm on n-Si and 200 nm on p-Si substrates, possess uniform size distribution and fully covers surfaces. X-ray diffraction (XRD) measurements show that the films are crystalline material and are preferably grown along (0 0 2) direction. The impact of thermal annealing in the temperature range of 150-800 °C on ZnO film properties has been carried out. Low-temperature photoluminescence (PL) spectra of the as-prepared ZnO/Si samples show the extremely high intensity of the near bandgap luminescence along with the absence of visible emission. The optical quality of ZnO thin films was improved after post-deposition thermal treatment at 150 °C and 400 °C in our experiments, however, the luminescence intensity was found to decrease at higher annealing temperatures (800 °C). The obtained results indicate that electrodeposition is an efficient low-temperature technique for the growth of high-quality and crystallographically oriented ZnO thin films on n-Si and p-Si substrates for device applications.