Zinc oxide arouses considerable interest since it has many applications—in microelectronics, environmental decontaminations, biomedicine, photocatalysis, corrosion, etc. The present investigation describes the green synthesis of nanosized ZnO particles using a low-cost, ecologically friendly approach compared to the classical methods, which are aimed at limiting their harmful effects on the environment. In this study, ZnO nanoparticles were prepared using an extract of Mentha arvensis (MA) leaves as a stabilizing/reducing agent, followed by hydrothermal treatment at 180 °C. The resulting powder samples were characterized by X-ray diffraction (XRD) phase analysis, infrared spectroscopy (IRS), scanning electron microscopy (SEM), and electron paramagnetic resonance (EPR). The specific surface area and pore size distribution were measured by the Brunauer–Emmett–Taylor (BET) method. Electronic paramagnetic resonance spectra were recorded at room temperature and at 123 K by a JEOL JES-FA 100 EPR spectrometer. The intensity of the bands within the range of 400–1700 cm⁻¹ for biosynthesized ZnO (BS-Zn) powders decreased with the increase in the Mentha arvensis extract concentration. Upon increasing the plant extract concentration, the relative proportion of mesopores in the BS-Zn samples also increased. It was established that the photocatalytic performance of the biosynthesized powders was dependent on the MA concentration in the precursor solution. According to EPR and PL analyses, it was proved that there was a presence of singly ionized oxygen vacancies (V₀⁺) and zinc interstitials (Zn_i). The use of the plant extract led to changes in the morphology, phase composition, and structure of the ZnO particles, which were responsible for the increased photocatalytic rate of discoloration of Malachite Green dye.