This paper reports the fabrication of a new micro/nano carbon architecture array which owns the characteristics of inner-porous, desired conductivity and large effective surface area. The micro/nano inner-porous carbon structures were fabricated for the first time, with ordinary and cost-effective processes, including photolithography, oxygen plasma etching and pyrolysis. Firstly, micro/nano hierarchical photoresist structures array was generated through photolithography and oxygen plasma etching processes. By introducing a critical thin-film spin-coating step, and followed with carefully pyrolyzing process, the micro/nano photoresist structures were converted into innerporous carbon architectures with good electric connection which connected the carbon structures array together. Probably the inner-porous property can be attributed to the shrinkage difference between positive thin film and negative photoresist structures during pyrolyzing process. It is demonstrated that the simple method is effective to fabricate inner-porous carbon structures with good electric connection and the carbon structures can be used as electrochemical electrodes directly and without the addition of other pyrolysis or film coating processes. The electrochemical property of the carbon structures has been explored by cyclic voltammetric measurement. Compared with solid carbon microstructures array, the cyclic voltammetry curve of inner-porous carbon structures shows greatly enhanced current and improved charge-storage capability, indicating great potential in micro energy storage devices and bio-devices.