Qualitative and quantitative analysis of samples require good judgment from the analysts. These two aspects in gamma spectrometric analysis of Proficiency Test and solid radioactive waste samples for the determination of radionuclides are discussed. It is vital to judge and decide what energy peaks belong to which radionuclides prior to the creation of customized radionuclide library for the analysis of specific samples. Corrections due to radionuclide decay and growth, and the half-life assigned to a particular radionuclide in the uranium and thorium series are also discussed. Discussion on judgment to confirm the presence of thorium in food samples based on gamma spectrometry and neutron activation analysis is also provided.