During decommissioning of a nuclear power plant, a large amount of radioactive waste is produced, and it is known to cost more than 300 billion won to dispose the waste. To reduce the disposal cost, it is essential to minimize the number of radioactive waste drums, which can be achieved by detecting and removing hotspot contaminations in the radioactive waste drums. Therefore, a Compton CT system for radioactive waste monitoring is under development, which provides the images of both the internal structure of the drum and the radioactive hotspot(s) in the drum. Based on the acquired information, the activity of hotspots can be estimated. The performance of the system is affected by various geometry factors. Therefore, it is essential to determine optimal configuration by evaluating the effects of the factors on the performance of the system. In the present study, we determined the optimum value of the factors and then predicted the performance of the optimized system by using a simulator based on the Geant4 Monte Carlo simulation. For optimization, the factors were evaluated in terms of structural similarity index measure (SSIM) and measurement time. The considered factors were the activity of the CT source, source to object distance (SOD), object to detector distance (ODD), and projection angle. The simulation result showed that the activities of the CT sources were determined as 23 mCi for 137Cs and 9.6 mCi for 60Co. The optimal SOD and ODD were 180 cm and 40 cm, respectively. The optimal projection angle was evaluated as 4° since it achieves the SSIM of 0.95 faster than other projection angles. With the optimized parameters, the performance of the system was evaluated using the IAEA gamma CT standard phantom containing a hotspot of 137Cs (7.02 μCi). The Compton image was reconstructed using the back-projection algorithm, and the CT image was reconstructed using the filtered back-projection algorithm. The result showed that the location of the hotspot in the Compton image was well identified at the true position. The acquired CT image also well represented the internal structure of the phantom, and the estimated mean linear attenuation coefficient value (μ= 0.0789 cm−1) of the phantom was close to the true value (μ= 0.0752 cm−1). In addition, the hotspot activity estimated by combining the information of the Compton image and CT image was 8.06 μCi. Hence, it was found that the Compton CT system provides essential information for radioactive waste drums.