An approach based on sequential extraction separation and the subsequent ICP-MS measurement was introduced to determine 99Tc in radioactive wastes. The radwastes were firstly alkaline-fused and the 99Tc was separated by a sequential solvent extraction prior to ICP-MS measurement. NaDDC was selected as a chelation reagent in the solvent extraction processes. The influence of HCl and matrix concentration on the recovery yield and the effectiveness of removing isobar and unwanted radionuclides, such as 137Cs, 54Mn, 60Co and 110mAg, were evaluated. The designed sequential extraction procedure was optimized by an extraction experiment. The proposed technique is proven to be a simple and practical alternative for 99Tc determination in low-level radioactive wastes; chemical separation of 99Tc can be simplified and preconcentration such as precipitation and/or ion exchange, before the solvent extraction, can be excluded.