Dihydroxyacetone is a good candidate to valorize the excess glycerol obtained as byproduct in biodiesel production. Crystallization is likely the key unit operation to obtain a high quality and pure dihydroxyacetone. The selection of an appropriate solvent for crystallization is not trivial and depends on multiple factors. At the present work a new solvent selection methodology, based on solvents relative comparisons, is described and applied to dihydroxyacetone crystallization as a case study. The procedure accounts not only for process factors such as solubility and yield, but also for cost, recycling, disposal, environmental, health and safety issues. Solubility and theoretical yield data for dihydroxyacetone in methanol, ethanol and 2-propanol were experimentally determined, while cost, life-cycle assessment, environmental, health and safety data of solvents were gathered from different bibliographic sources, software and databases. Among the solvents assessed, methanol resulted as the best overall choice for DHA crystallization. The methodology proved to be a suitable, simple and flexible procedure for solvent selection at the initial stages of the crystallization operation design, being able to be upgraded for advanced stages of the crystallization process development. (C) 2015 Elsevier Ltd. All rights reserved.