Design of direct ethanol fuel cell (DEFC) plays a key role in its viability. A novel tubular DEFC is proposed to reconstruct the conventional structure, and tubular cathode is prepared by gel injection molding with Mesocarbon microbeads (MCMB), graphite and NH4Cl with different contents as raw materials. Moreover, simulation on the mass transfer and electrochemical performance of DEFC with a wider range of cathode porosity is carried out. Experiment results indicates that the support has higher porosity and strength when the graphite doping and NH4Cl is 40% and 2%–10%, respectively. Furthermore, superior performance of cathode and DEFC electrical performance are perceived due to larger porosity, especially when the porosity is 0.5. Moreover, in the simulation the results also show that porosity of cathode diffusion layer (CCL) has a significant effect on the oxygen mass transfer and removal of liquid water. Larger porosity means better electrical performance and delivers more power, which is more obvious at 0.2–0.6. It is proved that when the porosity is about 0.5, comprehensive performance of tubular DEFC is better than other models.