Development of possible technologies for the generation of green energy is the focus of research worldwide. Fuel cells are a promising option in this regard. Out of the various categories of fuel cells, air breathing–direct methanol fuel cells (AB‐DMFCs) are finding a prominent place as an electric power source for charging of compact electronic devices. In AB‐DMFC, the design and construction of the cathode current collector is very crucial, since the cathode current collector performs important functions in the fuel cell operation such as collecting the electrons, facilitating the flow of oxygen for the cathode reaction and evacuating the water bubbles formed at the cathode side. An ideal current collector improves the cell performance multifold. The present paper deals about the performance of an AB‐DMFC fitted with three different cathode current collector designs, viz., a wire mesh current collector (WMCC) made of SS316L, WMCC with a supporting plate (SP) and a perforated current collector (PCC) with an open ratio of 45.40%. A single serpentine flow channel engraved on a graphite plate was used as the anode flow channel plate. Experimental investigations are carried out to examine the impact of the cathode current collector design on the performance of AB‐DMFC and also by varying the operating parameters of methanol flow rate and concentration. The next stage of the experiments are carried out with the addition of a liquid electrolyte layer (LE), which is kept between two half Membrane Electrode Assemblies. Experimental results reveal that the LE layer enhances the fuel cell performance compared to conventional AB‐DMFC.