Catalytic steam reforming of dimethoxymethane (DMM) to hydrogen-rich gas was successfully performed using structured CuO-ZnO/eta-Al2O3/FeCrAl catalysts. The catalysts containing on their surface both acidic and copper-based sites were active and selective for DMM steam reforming to hydrogen-rich gas with low (< 1 vol.%) CO content. In particular, the CuO-ZnO/eta-Al2O3/FeCrAl catalysts provided a 100% DMM conversion with hydrogen production rate of similar to 2500 ml H-2/(g(cat).h) at 300 degrees C, WHSV =3500 ml/(g(cat).h) and molar ratio H2O/DMM= 4.5.