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With advances in fabrication technologies, a number of methods can be used to create micro/nanostructures. Herein, a simple and efficient silicon nano-column array is made through self-assembled nano-sphere lithography (SANL) and catalytic etching. Moreover, we demonstrate the ability to apply this high aspect ratio structure into fuel cell electrodes. The experimental results indicate that SANL can effectively define a nano-patterned array. The highest height of nano-column is about 10 μm which were formed by catalytic etching with 25 min. Furthermore, nano-column arrays with catalytic etching of and 15 min were used to produce a fuel cell electrode. Its oxidation current of 6.04 mA is 8.1 times higher than that obtained by a planar electrode.