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The biomass-based platform molecule 2,3-butanediol (2,3-BDO) has a wide range of applications in production of sustainable fuels, chemicals, synthetic rubber, and others. However, the selective separation of 2,3-BDO from multicomponent fermentation broths presents challenges due to its low concentration, high solubility in water, high boiling point, and presence of many other species. Here we demonstrate remarkably selective enrichment and recovery of 2,3-BDO from a corn stover hydrolysate fermentation broth by a pure-silica nano-MFI-type zeolite adsorbent. By means of cyclic and simulated moving bed (SMB) adsorption processes, we obtained concentrated aqueous 2,3-BDO streams from the fermentation process stream with ~ 93% purity and 3-fold enrichment, and > 98% purity and 8-fold enrichment, respectively. These findings provide strong support for large-scale adsorptive separation for biobased 2,3-BDO production.