A laser-Raman spectrometric method was developed for the determination of polyatomic ions in alkaline high-level radioactive waste super-nates. From peak heights of well-resolved Raman hands, concentrations of NO2−, SO42−, CrO42−, PO43−, and Al(OH)4− ions are determined relative to NO3− ion concentrations in raw solutions. The concentration of an NO3− ion is determined independently by quantitative dilution of an aliquot with standardized 2M NaClO4. The relative precision at the 95% confidence level for a single determination is ±5%. Although Savannah River Plant waste samples are pale yellow and turbid, centrifugation clarifies them sufficiently for reproducible spectra to be recorded with 488-nm Ar+ excitation.