Dimethyl ether (DME) is expected as a clean fuel of the 21st century. I have developed new catalysts for hydrogen production by steam reforming of DME. Cu-Zn/Al2O3 catalysts prepared by a sol-gel method produce large quantities of H2 and CO2 by DME steam reforming under lower reaction temperature. H2 production by steam reforming of DME consists of two reaction steps. The first reaction is hydrolysis of DME into methanol. The second reaction is steam reforming of methanol that produces H2 and CO2. For this reason, the mixed catalysts of DME hydrolysis catalysts and methanol steam reforming catalysts are used for hydrogen production by DME steam reforming. However, the copper alumina catalysts prepared by the sol-gel method in single use are more excellent for H2 production by DME steam reforming than the mixed catalysts. The reason is that Al2O3 sites for DME hydrolysis and Cu sites for methanol steam reforming are co-existing closely on the catalyst surface. The consecutive reactions smoothly occur, and hydrogen is produced more effectively over the sol-gel Cu/Al2O3 in single use than over the mixed catalysts. Addition of Zn, Mn, or Fe into Cu/Al2O3 activates steam reforming of DME. The Cu-Zn(29-1wt.%)/Al2O3 catalyst showed the excellent activity of DME steam reforming; the DME conversion was 95%, H2 yield was 95%, and CO concentration was 0.8 mol.%. I have developed new catalysts for H2 production from DME, and the catalysts give us a great potential for H2 supply from DME.