The performance of practical-sized membrane-electrode assemblies (MEAs) using titanium nitride-supported platinum (Pt/TiN) as the cathode catalysts was evaluated with the use of a practical single cell designed for microscale combined heat and power (CHP) applications. The performance can be controlled by adding acetylene black (AB), with the behavior being dominated by the percolation law. The electrical resistance of the MEAs drastically decreased for AB contents greater than 37 vol%. The Pt utilization percentage was close to 100% for Pt/TiN with percolated AB networks. It was also found that the percolated AB networks supplied effective gas transport pathways, which were not flooded by generated water, thus enhancing the oxygen mass transport. The practical-sized MEA using Pt/TiN + 47 vol% AB showed 1.5 times greater mass activity and a comparable performance under a practical operating condition for micro-CHP applications, compared with the MEA using a commercial graphitized carbon black-supported platinum catalyst.