Scientific breakthroughs are occurring at an accelerated rate within the agricultural production, pretreatment, and enzymatic processing phases for bioethanol production processes.  At the same time, new technology for recovering and purifying the produced chemicals from the unique matrix of impurities present in the biomass feedstock production streams will be just as important.  Polyelectrolytes (high molecular weight charged polymers) can be used in several locations within a biorefinery, and offer tremendous potential for economical, multi-functional, and highly efficient separations.  We have shown that with the appropriate choice of polymer chemistry and dosage that solid-liquid clarification operations (centrifugation or filtration) can be enhanced dramatically.  At the same time, polyelctrolytes can also be used to selectively separate sugars from potential co-products (and inhibitory chemicals) such as organic acids, furfural, hydroxymethyl furfural, and phenolic compounds.  Finally, these polymers have the potential to be utilized as “lignin blockers” and/or rheological modifiers to facilitate enzyme recovery and higher solids loading. This presentation will provide an overview of applying polyelctrolyte operations to enhance separations within a lignocellulosic bioethanol production facility.  Current successes and challenges, along with future opportunities will be discussed.