In this work, ZnO NPs were successfully synthesized by the sol–gel method without any organic additives or post annealing. The effect of the preparation process on the structural and optical properties of the resulting NPs was investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy. The structural characterization demonstrated clearly that the NPs crystallize in pure ZnO würtzite structure without any other secondary phases. Furthermore, we show that it is possible to perform the control of the crystalline growth orientation of ZnO NPs, which is a key parameter when seeking to develop ZnO NPs with piezoelectric properties for nano-transducer applications. In fact, TEM observations show that the reduction of the NaOH flow changes the NPs shape from hexagonal NPS to short nanorods grown along the c-axis. The PL spectra of the obtained NPs excited at 280 nm, present an UV emission centered at approximately 380 nm with a slight shift when varying the synthesis temperature and/or the NaOH flow. Moreover, as the visible region (from 400 to 650 nm) is concerned, it was shown that the increasing of the synthesis temperature affects strongly the kind of interstitial defects (Oi, Zni and VoZni) formed in ZnO nanostructures. However, the excitation at 320 nm revealed a broad deep-level emission for all the samples that can be deconvoluted into two Gaussian peaks centered at 514 nm (P1) and 581 nm (P2). These last results have been discussed in the light of a physical mechanism based on the Schottky barrier.