In this study, electrodes of titanium dioxide nanotube arrays (TNAs) were successfully synthesized by applying the anodic oxidation etching method, as well as the use of green synthetic technology to add reducing agents of tea or coffee to reduce metal palladium from palladium chloride. Synthesis of palladium modified TNAs (Pd/TNAs) was conducted by the microwave hydrothermal method after the metal palladium was reduced. In order to identify the surface structure, light absorption and elemental composition, TNAs and Pd/TNAs were characterized by X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). Furthermore, to test the photocurrent density, electron resistance, and hydroxyl radicals by I-t plot, electrochemistry impedance spectroscopy (EIS), and electron paramagnetic resonance (EPR) were investigated. The photocurrent (4.0 mA/cm2) of Pd/TNAs-C (using coffee as the reducing agent) at +1.0 V (vs. Ag/AgCl) was higher than that of the pure TNAs (1.5 mA/cm2), illustrating that Pd/TNAs-C can effectively separate photogenerated electrons and holes. Pd/TNAs is a favorable material as a photoanode for the photoelectrochemical (PEC) removal of organic pollutants in wastewater.