The present work involves investigating an unexplored soft-chemical method for synthesizing nanostructured ZnO through biopolymer gelation. Our objective was to exploit (i) the difference in the gelation mechanism of four tested biopolymers, namely, alginate, chitosan, carboxymethylcellulose (CMC), and pectin and (ii) numerous experimental parameters that govern this process in order to allow the control of the growth of nanostructured ZnO, with a view to using the prepared oxides as photocatalysts for the oxidation of the Orange G dye. So, the effect of biopolymer's nature on the microstructural, morphological, and textural properties was examined by thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, field-emission gun-scanning electron microscopy-high resolution (FEG-SEM) with energy-dispersive spectrometry (SEM-EDS), ultraviolet-visible (UV-vis) spectroscopy, and N 2 adsorption/desorption. As-prepared oxides were crystallized in a hexagonal wurtzite structure, with a clear difference in their morphologies. The sample prepared by using chitosan has a specific surface area of around 36.8 m 2 /g in the form of aggregated and agglomerated nanostructured minirods and thus shows the best photocatalytic performance with 99.3% degradation of the Orange G dye in 180 min.