Potassium nickel hexacyanoferrate KNi[Fe(CN)6] (NiHCF) was synthesized by a simple co-precipitation method and investigated as a cathode material for lithium-ion batteries. The X-ray diffraction and transmission electron microscopy studies revealed the formation of pure phase of agglomerated NiHCF nanoparticles of about 20–50nm in size. The material exhibited stable cycling performance as a cathode in a lithium half-cell within a wide range of current densities, and a working potential around 3.3V vs. Li+/Li. The lithium ion diffusion coefficient in this system was determined to be in a range of 10−9 to 10−8 cm2 s−1, which is within the values for the cathode materials for lithium-ion batteries with high rate capability. Considering promising electrochemical performance and attractive lithium-ion diffusion properties of this material along with its economical benefits and simplified preparation, NiHCF could be considered as a very promising cathode for large scale lithium-ion batteries.