For the peaceful use of nuclear energy, the international community has devoted itself to fulfilling its obligations under the Safeguards Agreement with IAEA. In this regard, uranium in a radioactive waste drum should be analyzed and reported in terms of mass and 235U enrichment. In order to characterize radioactive wastes, gamma spectroscopy techniques can be effectively applied. In the case of high-resolution gamma spectroscopy, because an HPGe detector can provide excellent energy resolution, it can be applied to analyze a mixture having a complicated isotopic composition. However, other substances such as wood, concrete, and ash are mixed in radioactive waste with various form factors; hence, the efficiency calibration is difficult. On the other hand, In Situ Object Counting System (ISOCS) has a capability of efficiency calibration without standard materials, making it possible to analyze complex radioactive wastes. In this study, the analysis procedure with the ISOCS was optimized for quantification of radioactive waste. To this end, a standard radioactive waste drum at KEPCO NF and low-level radioactive waste drums at Korea Radioactive Waste Agency (KORAD) were measured. The performance of the ISOCS was then evaluated by Monte Carlo simulations, Multi-Group Analysis for Uranium (MGAU) code, and destructive analysis. As a result, the ISOCS showed good performance in the quantification of uranium for a drum with the homogenized simple geometry and long measurement time. It is confirmed that the ISOCS gamma spectroscopy technique could be used for control and accountancy of nuclear materials contained in a radioactive waste drum.