We investigated the catalyst that promotes the selective dehydration of 2,3-butanediol to 1,3-butadiene. We found that the SiO2-supported CsH2PO4 catalyst showed the highest 1,3-butadiene selectivity (>90%) with the single-bed catalyst system. The present process was successfully applied to bio-based 1,3-butadiene production from 2,3-butanediol produced by the microbial fermentation of biomass resources.