Without any external ligands as additives, the observation revealed that the simple acid hydrolysis resulted in predominantly hematite formation, i.e., α-Fe2O3 (red-brown solid), while base hydrolysis resulted in the magnetite (Fe3O4,) formation, i.e., a blackish-red solid (Fig. .0). This is also much more facile than base hydrolysis due to the presence of excess H + ions in the solution. However, perturbation of the same system by changing the ligands, i.e., pure chemical surfactants as well as biogenic extract, significantly affected the nanocrystal's shape along with the polymorphic forms. Moreover, polymorphism in iron oxides is reported to be a temperaturedependent phase transition under laboratory conditions. However, base hydrolysis, on the other hand, involves relative difficulty in sol formation. This is primarily due to excess OH -ions, favoring the formation of various complexes that allow the partial dissolution of the seeds, delaying the precipitation process. This, in turn, affects the whole seeding and nucleation processes. Interestingly, the resultant oxide, in the case of base hydrolysis, is predominantly magnetite (Fe3O4,), i.e., a blackish-red solid (Fig. .0). Thus, the simple base hydrolysis remained an ineffective process with poor recovery of an impure and different oxide (Fe3O4), as shown in diffractogram (Fig. .0 and 2.1). Thus, for methodological purposes, unless required otherwise, it can be inferred that, unlike the synthesis of zinc oxide and many other metal oxides, the base hydrolysis for Fe2O3 synthesis using the sol-gel process is an undesirable choice. Nevertheless, this observation underlines the role of solution pH in the laboratory synthesis of iron oxide and its probable importance during mineral (iron) precipitation in natural environments. Moreover, beyond the differences in solution phase evolutionary pathways, the sintering of all the samples at a fixed temperature (500 ˚C) in a muffle furnace retains the relative effect of the ligands. In summary, the XRD (Fig. .0, 2.1 & Table ) confirms that except for unperturbed base hydrolysis (Fe-BH), the samples resulted in predominantly hematite (Fe2O3) nanoparticles with varying size, morphology, and even polymorphic forms. Further, based on the size calculated using the Debye-Scherrer Equation ( ), the differential effect of the ligands on the size of the nanocrystals is apparent. For instance, the average crystallite size (Table ) varied in the range of ~20.0 nm to ~55.0 nm, with FeCT being the smallest, followed by FeMC and then FePM with respect to FeBH.