Technetium-99 (Tc), a high yield fission product generated in nuclear reactors, is one of the most difficult contaminants to address at the U.S. Department of Energy Hanford, Savannah River, and other sites. In strongly alkaline solutions typifying Hanford tank waste, Tc exists as pertechnetate (TcO4-) (oxidation state VII) as well as in reduced forms (oxidation state < VII), collectively known as non-pertechnetate (non-TcO4-) species. Designing strategies for effective Tc management, including separation and immobilization, necessitates understanding the molecular structure of the non-TcO4- species and their identification in actual tank waste samples. Identification of non-TcO4- species would facilitate the development of new treatment technologies effective for dissimilar Tc species. Toward this objective, a spectroscopic library of the Tc(I) [fac-Tc(CO)3]+ and Tc(II, IV, V, VII) compounds was generated and applied to the characterization of the actual Hanford AN-102 tank waste supernatant, which was processed to adjust Na concentration to ∼5.6 M and remove 137Cs by spherical resorcinol-formaldehyde (sRF) ion-exchange resin. Post 137Cs removal, the cesium-loaded sRF column was eluted with 0.45 M HNO3. As-received AN-102, Cs-depleted effluent, and sRF eluate fractions were comprehensively characterized for chemical composition and speciation of Tc using 99Tc nuclear magnetic resonance spectroscopy and X-ray absorption spectroscopy. It was demonstrated for the first time that non-TcO4- Tc present in the AN-102 tank waste is composed of several low-valent Tc species, including the Tc(I) [fac-Tc(CO)3]+ and Tc(IV) compounds. This is the first demonstration of multiple non-TcO4- species co-existing in the Hanford tank waste, highlighting their importance for the waste processing.