Polarized neutron reflectivity has been measured for the CoFe/TiZr alloy multilayers. The results show that: (a) The reflectivity behavior of the sample with un-equal-thickness bilayer (type B) is better than that of the sample with equal-thickness bilayer (type A). The former performs better in producing neutron guide, (b) The best annealing temperature is about 250°C for the sample of type A, however, the structures of both type A and type B samples change apparently after 350°C annealing. (c) Different from the type B sample, the first Bragg peak position for the type A sample moves along Q axis, indicating that the period of the multilayer varies in a way of increase-decrease-increase with the increase of annealing temperature.