The influence of predominant native defects in forming ZnO with p-type conductivity is discussed in this work when the semiconductor is synthesized only in water. The semiconductor was prepared by dissolving a Zn-salt in deionized water at 80 °C. The powders were thermally treated at 400 °C in an air atmosphere to obtain well-defined crystalline ZnO. XRD, SEM, EDS, Raman spectroscopy, diffuse reflectance, photoluminescence, and Seebeck effect techniques were used to characterize the synthesized material. The results showed a well-crystalline semiconductor in wurtzite phase. The crystal-oriented growth was the (002) plane. The sample morphology was formed by highly ordered sticks-like. The optoelectronic characterization showed that the synthesized ZnO had a lower band gap than that reported in the literature. It was related to deep energy levels corresponding to oxygen interstitials as the predominant native defects. Raman, EPR, and photoluminescence spectra analysis corroborated the existence of native defects in the crystalline structure. The p-type conductivity of the sample was determined by Seebeck coefficient analysis. A synthesis reaction mechanism involving the formation of oxygen interstitials was proposed in this work. Understanding the effects of native defects in wide band gap semiconductors is necessary to design new materials for sensors or energy conversion applications.