Radioactive wastes that are generated as a result of operating NPPs, contain 63Ni and 59Ni that should be analyzed in accordance with the notice of Nuclear Safety and Security Commission (NSSC) for the acceptance of Korea Radioactive Waste Agency (KORAD). Analyzing 63Ni and 59Ni has few challenges to determine activities of each nuclide in radioactive waste sample that contains both nuclides. As is well known, 63Ni can be analyzed by liquid scintillation counter (LSC) detecting its emitted beta rays, however, beta rays emitted from 59Ni are overlapped on the spectrum. Therefore, to discriminate those two nuclides, spectrum channel should be divided according to its dedicating part of the spectrum. For instance, 59Ni contribute to spectrum channel 30–250, on the other hand, 63Ni contributes to spectrum channel 30–450. In other word, 63Ni solely can be analyzed on the channel from 260 to 450. To analyze both 63Ni and 59Ni using this channel division method, detection efficiency must be measured in advance; efficiency of 63Ni and 59Ni at ch. 30–250, and efficiency of 63Ni at ch. 260–450, then the activity can be calculated using the corresponding efficiency. In this study, for verifying the feasibility of channel division method, 5 simulated samples were prepared with different ratio of 63Ni/59Ni. The ratio varies as 1, 2, 10, 20 and 100 spiking standard source of 63Ni and 59Ni. Each sample was mixed with scintillation cocktail and detected for 90 minutes by LSC (300SL, Hidex) after the stabilization of solutions. As a result, calculated 63Ni activities for all sample were averaged as 97% of spiked activity. However, calculated 59Ni activity were 101%, 103%, 128%, 140%, 260%, respectively. The result indicates that 59Ni cannot be discriminated by channel division method when it exists in the sample with high 63Ni over 10 times then 59Ni such as radioactive waste sample. However, the results also show that the channel division method for analyzing 63Ni activity was successful verifying it can determine the activity of 63Ni regardless of the affect of 59Ni on the spectrum.