Abstract Spinel‐structured transition metal (TM) oxides have shown great potential as a sustainable alternative to platinum group metal‐based electrocatalysts. Among them, high‐entropy oxides (HEOs) with multiple TM‐cation sites are suitable for engineering octahedral redox‐active centers to enhance the catalyst reactivity. This paper reports on the preparation of electrospun (Cr 1/5 Mn 1/5 Fe 1/5 Co 1/5 Ni 1/5 ) 3 O 4 nanofibers (NFs) and their evaluation as electrocatalysts. Its main aim is to unveil the nanostructural features that play a key role in the alkaline oxygen evolution reaction. Differing calcination temperature (300−800 °C) and duration (2 or 4 h) leads to different morphology of the NFs, crystallinity of the oxide, density of defects, and cation distribution in the lattice, which reflect in different electrocatalytic behaviors. The best performance (overpotential and Tafel slope at 10 mA cm −2 : 325 mV and 40 mV dec −1 , respectively) pertains to the NFs calcined at 400 °C for 2 h. To gain a deeper understanding of their electrocatalytic properties, the pristine NFs are investigated by a combination of analytical techniques. In particular, broadband electric spectroscopy reveals that the mobility of oxygen vacancies in the best electrocatalyst is associated to very fast local dielectric relaxations of metal coordination octahedral geometries and experimentally demonstrates the key role of O‐deficient octahedra.

Interplay Between Calcination Temperature and Alkaline Oxygen Evolution of Electrospun High‐Entropy (Cr1/5Mn1/5Fe1/5Co1/5Ni1/5)3O4 Nanofibers