A Pd-Ni nanoparticle modified silicon-based anode is fabricated and the possibility of using it for the direct alkaline fuel cell of carbohydrates has been investigated by electrochemical method. Upright and porous ordered silicon nanowires (SiNWs) arrays are prepared by wet etching. The Pd-Ni nanoparticles are covered to the SiNWs uniformly by chemical deposited successively. Using six kinds of common carbohydrate, including glucose, fructose, maltose, lactose, sucrose, and starch, as testing subjects, the performance of electrocatalytic oxidation is studied. Experiment results show that the electrochemically active surface area of Pd-Ni/SiNWs electrode electrochemically active surface area is 53.482 cm2, and higher electrocatalytic activity and stability is displayed for the direct oxidation of glucose, fructose, maltose, and lactose. Firstly, the Pd-Ni/SiNWs electrode has better electrochemical performance for carbohydrates and is promising for applications in direct alkaline fuel. Secondly, more kinds of carbohydrates might potentially use as energy source for direct alkaline fuel.