NPs, have been synthesized by acid (FeAH), and base (FeBH) hydrolysis without any external capping agent in the first attempt. We then followed the acid hydrolysis protocol, varying the additives, namely the methylcellulose (MC), cetyltrimethylammonium bromide (CTAB), and PM extract. The process was aqueous sol-gel at room temperature (35°), with precursor (FeSO4.7H2O) salt, and all other reaction conditions being the same as illustrated in Scheme 1 and Table . The choice of analytical grade surfactants along with biogenic extract (PM) was designed to investigate the effect of ligand-based perturbation on the overall synthetic outcome of the reaction in general and the shape anisotropy of the resulting nanoparticles in particular. The use of biogenic extract of a lignocellulosic waste (PM), along with chemically pure surfactants like CTAB and MC, was to understand the possible role of humic substances during the evolution of crystalline stages of minerals in natural scenarios with reference to laboratory scale well-defined systems. For instance, secondary mineral formation occurs in geological and soil environments in the presence of degraded organic substances from vegetable sources. In addition to this, two separate schemes of simple base hydrolysis (FeBH) and acid hydrolysis (FeAH), without any ligand, were also taken to assess the exclusive role of the capping ligands (natural and synthetic) on the evolution of crystalline phases and pathways. The overall synthetic part of the experiment is designed to understand the evolution of the shape and forms of iron oxides (Fe2O3) in the presence of external ligands as solution phase additives under a sol-gel synthesis scheme. This is followed by the study of their photocatalytic behaviour under tropical sunlight.