Compositional-variation-induced CoFe-LDHs (with various Co:Fe ratio; LDH, layered double hydroxide) have been prepared via a simple wet-chemical method followed by the formation of 1D microfibers through electrospinning (ES) techniques. The as-synthesized 1D fiber with a Co/Fe ratio corresponding to a 0.5:1 microfiber (CoFe-LDH_0.5 fiber) showed the highest oxygen evolution reaction (OER) activity by demanding an overpotential value of 267 mV while the corresponding powder material demands an overpotential value of 312 mV at pH = 14. In addition, the neutral OER  activity of the catalysts was also verified in 0.2 M phosphate buffer solution (PBS), and the same CoFe-LDH_0.5 fiber demands a lower overpotential value of 300 mV while the CoFe-LDH₁ fiber and  CoFe-LDH_1.5 fiber demand 320 and 340 mV overpotential, respectively. Hence, we have obtained the interesting result that the incorporated 1D fibrous material with lower cobalt content showed a higher activity than the other fibrous materials. A magnetic study shows that the presence of cobalt ions with a lower concentration ensures the higher ferromagnetic (FM) interaction among the cobalt ions which in turn polarize the overall electronic spin of the hydroxide entity. The  polarization of the electronic spin results in lowering the energy barrier by omitting the spin inversion barrier.