Freeze-dried macroporous solid foams were prepared from the multi-walled carbon nanotube (MWCNT) aqueous suspensions dispersed by chitosan. Thin film shaped CNT solid foams were prepared, and applied to the gas diffusion layers (GDLs) of a laboratory scale proton exchange membrane fuel cell (PEMFC). It was demonstrated that the prepared carbon foams in this study were useful to a fuel cell GDL material. The prepared cell performances were fairly comparable to the cell prepared with conventional carbon paper for GDL material. The microstructures of the prepared carbon foams were found to affect on the PEMFC performances. It was suggested that the interconnected carbon networks formed during the freezing step closely link to the cell performances. Hence, the defection of the interconnected microstructure lead degradation of the GDL quality. The impedance measurement made clear that the prepared foam materials were also advantageous for reducing the ohmic resistance in PEMFC assembly. The kinetic resistance values and the thermal conductive characteristics suggested that the freezing process would also control the degree of overlaps among single CNTs in a freeze-dried bulk that influenced on the electrochemical properties.