Electroless Ni68Co24P8 coatings were synthesized on p-type Si<100>substrates. Microstructures corrosion resistane and magnetic property of Ni68Co24P8 coatings were investigated. The results indicate that an amorphous phase for Ni68Co24P8 coatings with 0.5~4.2 μm nodule clusters distributes uniformly on the coating surface. In 10.0%NaOH and 3.5% NaCl solutions Ni68Co24P8 coatings show an active-passive-transpassive behavior. However, in 1.0%H2SO4 solution, no passivation films can be formed and the corrosion resistance of the coatings is decreased prominently. Furthermore, the Ni68Co24P8 coatings exhibite typical soft-magnetic characterization and the saturation magnetization is 33.4 A·m2/kg.