The electronic structures and optical properties of various sizes of ZnO quantum dots (QDs) were studied using x-ray absorption, photoluminescence, and Raman spectroscopy. The increase in the intensity ratio of the second-order Raman spectra of longitudinal optical mode and its fundamental mode, which is related to the strength of the electron-phonon coupling (EPC), is found to increase with the size of QD. The trend of EPC also correlates with the increase of the intensity ratio of the O 2pπ (Iπ) and 2pσ (Iσ) orbital features in the O K-edge x-ray absorption near-edge structure (XANES) as the size of QD increases. The EPC and XANES results suggest that the crystal orientations of ZnO QDs are approximately aligned with the c axis parallel with the polarization of x-ray photons.