Nanoplate to pseudocubic-shaped hematite (α-Fe 2 O 3 ) nanoparticles along with the gradual engravement of tetrahedral Fe 3+ has been synthesized by controlling the precursor (FeCl 3 •6H 2 O) concentration from 0.005 M (A 1 ) to 0.2 M (A 4 ). The role of the surfactant polyvinylpyrrolidone on the preferential plane ([110] to [012]) growth and highly energetic tetrahedral Fe 3+ phase (increases 2.7 times for A 4 than A 1 ) nucleation over the hematite surface has been elucidated from the HRTEM images, XPS, and Raman spectroscopy. This tetrahedral phase and the morphology variation facilitate the Fe−Fe interaction significantly, which improves the saturation magnetization from 0.13 emu/g (A 1 ) to 0.37 emu/g (A 4 ). Stronger magnetic d−d coupling in the A 4 sample promotes dominant photoluminance (PL) spectra. It also exhibits linear dependence with the excitation wavelength (300−380 nm) that can be exploited in the design of a UV detector. The supercapacitive performance of ethylene glycol supported PEDOT-PSS-α-Fe 2 O 3 composite films as negative electrode materials, in the voltage window of −1.3 to −0.5 V, suggests this material to be a promising candidate for the next-generation charge storage devices. The sample engraved with the richest Fe 3+ ions shows the highest specific capacitance of 705.7 F/g in 2 M SO 3 2− electrolytes, and its cyclic stability increases to 111% over 1500 cycles.