Today, most technologies used to fractionate plant materials are based on expensive chemical processes that often have negative environmental impacts by consuming water, energy, and solvents and creating large quantities of effluents. In addition, during the separation step, the major components are often partially degraded. Achieving high fractionation yields while maintaining the integrity of the macromolecular structure is a major challenge for the next generation of biomass refining processes. Electrostatic separation (ES), which enables the production of enriched fractions in compounds of interest while preserving their (native) functionalities has emerged as an ecofriendly biotechnology for the fractionation of agro-resources in dry conditions. In this review, the potential of ES in a biorefinery scheme is evaluated and the technological obstacles that still need to be overcome for its full deployment at industrial scale are identified.