In this paper, ZnO nanoparticles (NPs) were greenly synthesized at different pH values of 4, 6, 9.5, and 11 via Portulaca oleracea leaf extract, and the effect of pH on the optical and structural properties was studied. UV-Vis spectrophotometers and FTIR spectroscopy characterized the optical properties. Meanwhile, the structural properties were characterized via Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). Furthermore, their photocatalytic dye degradation was examined against methyl orange dye. The characterization results have confirmed the successful biosynthesis of ZnO nanoparticles with a size ranging between 22.17 to 27.38 nm. The synthesis pH value significantly influenced ZnO NPs’ optical and morphological properties. The results have also indicated the high performance of the greenly synthesized ZnO NPs for dye degradation.