Dimethyl ether (DME) partial oxidation (PO) was studied over 1 wt% Rh/Ce0.75Zr0.25O2 catalyst at temperatures 300–700 °C, O2:C molar ratio of 0.25 and GHSV 10000 h−1. The catalyst was active and stable under reaction conditions. Complete conversion of DME was reached at 500 °C, but equilibrium product distribution was observed only at T ≥ 650 °C. High concentration of CH4 and low contents of CO and H2 were observed at 500–625 °C 75 cm3 of composite catalyst 0.24 wt% Rh/Ce0.75Zr0.25O2/Al2O3/FeCrAl showed excellent catalytic performance in DME PO at O2:C molar ratio of 0.29 and inlet temperature 840 °C which corresponded to carbon-free region. 100% DME conversion was reached at GHSV of 45,000 h−1. The produced syngas contained (vol. %): 33.4 H2, 34.8 N2, 22.7 CO, 3.6 CO2 and 1.6 CH4. Composite catalyst demonstrated the specific syngas productivity (based on CO and H2) in DME PO of 42.8 m3·Lcat −1·h−1 (STP) and the syngas productivity of more than 3 m3·h−1 (STP) that was sufficient for 3 kWe SOFC feeding. PO of natural gas and liquified petroleum gas can be carried out over the same catalyst with similar productivity, realizing the concept of multifuel hydrogen generation. The syngas composition obtained via DME PO was shown to be sufficient for YSZ-based SOFC feeding.