A study on the ability of new microbial strains to assimilate biodiesel-derived glycerol at low purity (75%w/w) and produce extra-cellular platform chemical compounds of major interest was carried out. After screening several bacterial strains under different fermentation conditions (e.g., pH, O2availability, glycerol purity), three of the screened strains stood out for their high potential to produce valued-added products such as 2,3-butanediol (BDO), 1,3-propanediol (PDO) and ethanol (EtOH). The results indicate that under aerobic conditions,Klebsiella oxytocaACA-DC 1581 produced BDO in high yield (YBDO/Gly= 0.46 g/g, corresponding to 94% of the maximum theoretical yield; Ymt) and titer, while under anaerobic conditions,Citrobacter freundiiNRRL-B 2645 andEnterobacter ludwigiiFMCC-204 produced PDO (YPDO/Gly= 0.56 g/g, 93% of Ymt) and EtOH (YEtOH/Gly= 0.44 g/g, 88% of Ymt), respectively. In the case ofC. freundii, the regulation of pH proved to be mandatory, due to lactic acid production and a subsequent drop of pH that resulted in fermentation ceasing. In the fed-batch culture ofK. oxytoca, the BDO maximum titer reached almost 70 g/L, the YBDO/Glyand the mean productivity value (PrBDO) were 0.47 g/g and 0.4 g/L/h, respectively, while no optimization was imposed. The final BDO production obtained by this wild strain (K. oxytoca) is among the highest in the international literature, although the bioprocess requires optimization in terms of productivity and total cost. In addition, for the first time in the literature, a strain from the speciesHafnia alvei(viz.,Hafnia alveiACA-DC 1196) was reported as a potential BDO producer. The strains as well as the methodology proposed in this study can contribute to the development of a biorefinery that complements the manufacture of biofuels with high-value biobased chemicals.