The composition and performance optimisation of cathode catalyst platinum and catalyst layer structure in a proton exchange membrane fuel cell has been investigated by including both electrochemical reaction and mass transport process. It is found that electrochemical reactions occur in a thin layer within a few micrometers thick, indicating ineffective catalyst utilization for the present catalyst layer design. The effective use of platinum catalyst decreases with increasing current density, hence lower loadings of platinum are feasible for higher current densities of practical interest without adverse effect on cell performance. The optimal void fraction for the catalyst layer is about 60% and fairly independent of current density, and a 40% supported platinum catalyst yields the best performance amongst various supported catalysts investigated. An optimal amount of membrane content in the void region of the catalyst layer exists for minimum cathode voltage losses due to competition between proton migration through the membrane and oxygen transfer in the void region. The present results will be useful for practical fuel cell designs.