Ammonia has a substantial role in agriculture and the next generation of carbon-free energy supply. Electrochemical nitrate reduction into recyclable ammonium under benign conditions is significant. However, the development of such a process has been retarded by the lack of efficient electrocatalysts for highly selective synthesis of ammonia from wastewater. In this work, used to highly conductivity of carbon cloth as a substrate, morphology controlled of TiO₂ nanorods and hybrid nanostructure of nanorods with oxygen vacancies exhibit the microstructure characterization and surface defects and electrochemical charge dynamics characterization that compare with the nanoparticle. Herein, comparison wastewater to ammonia performance all samples, hybrid nanostructure of nanorod is showed to exhibit high faradaic efficiency (86.8 %) and selectivity (81.5 %) at - 0.6 V versus reversible hydrogen electrode from electrochemical nitrate reduction reaction and photoelectrochemical nitrate reduction reaction exhibit high faradaic efficiency (95.1 %) at - 0.5 V versus reversible hydrogen electrode in 0.1 M NaOH with 0.1 M NO₃-. Additionally, PEC-NO₃RR was conducted to confirm that light assists to produce ammonia yield and Faradaic efficiency.