In summary, our study provides a deeper understanding of the shape anisotropy evolution in iron oxide nanocrystals under the influence of naturally relevant organic ligands, framed within the principles of non-classical crystallization theory. The observed transformations from spherical to sheet-and rod-like structures highlight the role of sugar press mud ligands in directing nanocrystal growth. Furthermore, our electro-analytical approach reveals that variations in photocatalytic efficiency are more accurately described by electrochemical parameters such as the EPZC, 𝛷 𝑎𝑑 0 and ESCA, rather than conventional band gap and charge carrier dynamics.