Electrochemical converters (electrolyzers, fuel cells, and batteries) have gained prominence during the last decade for the unavoidable energy transition and the sustainable synthesis of platform chemicals. One of the key elements of these systems is the electrode material on which the electrochemical reactions occur, and therefore its design will impact their performance. This review focuses on the electrospinning method by examining a number of features of experimental conditions. Electrospinning is a fiber-spinning technology used to produce three-dimensional and ultrafine fibers with tunable diameters and lengths. The thermal treatment and the different analyses are discussed to understand the changes in the polymer to create usable electrode materials. Electrospun fibers have unique properties such as high surface area, high porosity, tunable surface properties, and low cost, among others. Furthermore, a little introduction to the 5-hydroxymethylfurfural (HMF) electrooxidation coupled to H2 production was included to show the benefit of upgrading biomass derivates in electrolyzers. Indeed, environmental and geopolitical constraints lead to shifts towards organic/inorganic electrosynthesis, which allows for one to dispense with polluting, toxic and expensive reagents. The electrooxidation of HMF instead of water (OER, oxygen evolution reaction) in an electrolyzer can be elegantly controlled to electro-synthesize added-value organic chemicals while lowering the required energy for CO2-free H2 production.