Extraction of californium/III/ with di-/−2-ethylhexyl/ phosphoric acid /D2EHPA/ in heptane from pyrophosphate media is almost quantitative between pH 4 and 5. From tripolyphosphate media, however, two to three extractions are needed in the pH range of 3–5 to isolate Cf3+ completely. Reextraction experiments show that 1M H2SO4 can back-extract Cf3+ completely while two to three reextractions with 5M HNO3 can only separate californium/III/. Reverse phase partition chromatography experiments were performed to recover 300 μg of californium/III/. From slope analysis of the extraction data the composition of the extracted species has been found to be Cf/H2P2O7/A.HA and Cf/H4P3O10/.A2.2HA from pyrophosphate and tripolyphosphate solutions, respectively, where D2EHPA is abbreviated as /HA/2.