Abstract Complex formation reactions of praseodymium nitrate hexahydrate, and neodymium nitrate hexahydrate salts with tri-n-butyl phosphate (TBP) and several other neutral organophosphorus reagents were investigated in supercritical carbon dioxide. The concentration of the metal complexes in the supercritical fluid (SCF) phase was determined using UV-Vis and luminescence spectroscopies. The stoichiometry of the complexes was determined using the mole-ratio method. Extraction equilibrium constants were calculated from the spectral data using least-squares regression and hard-equilibria models. UV-Vis absorbance data indicate that praseodymium nitrate and neodymium nitrate both form 1:4 lanthanide–tributyl phosphate complexes in supercritical carbon dioxide at 308 K. The conditional extraction coefficients for those two systems were calculated to be log Kex=7.45±0.06 for the praseodymium system and log Kex=7.52±0.03 for the neodymium system. For comparison, neodymium nitrate complexation reactions with tri-n-butyl phosphate and tributyl phosphite (TBPO3) were studied in hexane under ambient conditions. UV-Vis data indicate that a 1:4 neodymium–tributyl phosphate complex is formed in hexane with a conditional extraction coefficient of log Kex=3.4±0.2. Tributyl phosphite forms a 1:8 complex with neodymium in hexane with a conditional extraction coefficient of log Kex=11.0±0.1. Neodymium nitrate was titrated with other organophosphorus reagents, tributyl phosphite and tributyl phosphine oxide (TBPO), in supercritical carbon dioxide to investigate differences between neutral oxygen donor ligands and neutral phosphorus donor ligands. UV-Vis and luminescence data indicate that neodymium nitrate forms a 1:8 complex with tributyl phosphite and a 1:5 complex with tributyl phosphine oxide, compared to a 1:4 complex with tri-n-butyl phosphate. The conditional extraction coefficient for the 1:8 neodymium–tributyl phosphite system was calculated as log Kex=21.4±0.2 from UV-Vis data, and log Kex=19.8±0.2 from luminescence data. The conditional extraction coefficient for the 1:5 neodymium–tributyl phosphine oxide complex was calculated as log Kex=7.83±0.05.