Abstract: A reliable procedure for determination of plutonium and total alpha activity in spent TBP/kerosene is developed. Since the creeping property of kerosene on heating TBP/kerosene specimen for alpha counting cannot be directly prepared by simple heating-evaporation. In this work kerosene is safely removed by distillation without loss of alpha activity. TBP is then carbonized by treatment with concentrated H_2SO_4 and thoroughly digested with HNO_3-HClO_4 mixture. Plutonium is separated from other alpha emitters by anion-exchange chromatography after oxidation state adjustment and quantified by a large area grid ionization chamber alpha spectrometer. The recovery of (chromatographic) separation is standardized to be (102±3.5)% by triplicate reference runs. The total alpha activity is measured in a similar way, but without carbonization and chromatographic separation. In this case a correction for self-absorption has to be made. The self-absorption coefficient is obtained by (comparison) of~(239,240)Pu activities measured with and without carbonization and chromatographic separation for the same sample. In addition a continuously decreasing alpha activity profile along the depth in a TBP/kerosene container is observed.