The highly ordered Si nanotube (SiNT) arrays have been fabricated and demonstrated to be an attractive matrix to accommodate macromolecules, such as proteins, and exhibit facile direct electrochemistry of cytochrome c without any pretreatment. A pair of well-defined redox waves can be observed in the aqueous solution containing cytochrome c on this SiNT electrode using cyclic voltammetry. The peak separation (Delta E-p) between the anodic and the cathodic peaks is 63 mV at the sweep rate of 10 mV/s, and the peak current is proportional to the square root of the sweep rates, which indicates that the redox process is a quasi-reversible process. The experimental results show that the good biocompatibility and nanoscale hollow structure of the SiNT arrays can be applicable to preparing Si-based biosensors and protein characterizations.