Abstract: The concentration of Tc in technetium scrubbing section (TcS) is an important parameter in the spent fuel reprocessing. This work aims at the TcS point in PUREX process, and with the partial least square (PLS) and Raman spectroscopy the calibration models are established for the determination of pertechnetate. The results show that, the root mean square error of calibration (RMSEC) is 0.005, and the root mean square error of prediction (RMSEP) is 0.004 with the correlation coefficient of 0.999 3. The limit of detection of this method is 0.015 g/L, and the precision is better than 5%(n=6). In addition, the influence of UO²⁺₂ on the determination of Tc was studied in this work. It is found that there is no significant influence on the determination of Tc for the mass concentration of U ranging from 25.00 to 50.00 g/L. This method is very fast and needs no pretreatment. It can be applied to the quantitative determination of Tc in TcS potentially.