This paper investigates the interesting effects of structural diversity and operating orientation on the performance of a liquid-fed passive air-breathing direct methanol fuel cell (PAB-DMFC). The results indicate that a higher thickness of the GEFC (R)-10N membrane helps enhance the cell performance due to its ability in reducing methanol crossover (MCO). When the cell uses carbon cloth at the anode but carbon paper at the cathode as the diffusion media, it produces higher performances than other combinations. The work also confirms the merit of using a cathode diffusion layer since it improves water, methanol and heat management. As for the structural optimization of current collector, it is recommended to use the circular-hole-array pattern with a lower open ratio at the anode but the parallel-fence pattern with a higher open ratio at the cathode. It is further demonstrated that the vertical operation yields a higher cell performance at a lower methanol concentration while the horizontal operation performs better at a higher methanol concentration. Besides, the effects of opening pattern and working orientation on the CO2 evolvement behaviors are analyzed by using visualized methods. Detailed mechanisms related to the resultant phenomena are comprehensively provided in this work. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.