In this work, well-aligned and ordered NiSi nano columnar arrays were fabricated using an ion assisted oblique angle deposition technique based on electron beam co-evaporation. It was demonstrated that these NiSi nano columnar arrays were promising high-capacity anode material for next generation lithium-ion batteries. Nano-structured Si films were also deposited and evaluated as anode material under the same experimental conditions for comparison. It was found that the dopant of about 9% wt. Ni in Si nano columns helped to improve the electrical conductivity and the electrochemical performance of the material. The electrochemical characterization showed that the well-aligned nano-columnar porous NiSi thin film delivered a very high reversible capacity (~1100mAhg−1) with almost no capacity fade for up to 100 cycles.