The study of the chemical behavior of uranium in biological medium is still of great interest. By the use of capillary electrophoresis (CE) and time-resolved laser-induced fluorescence (TRLIF), it is possible to characterize the different complexes of uranium. Hence, CE, using the isoelectric focusing mode (CIEF), allows for the separation of the different complexes as a function of their isoelectric points (pI) and TRLIF as a speciation method leads to the identification at very low level of different uranyl complexes by temporal resolution and spectral deconvolution. Results obtained on various inorganic chemical systems (phosphate, bicarbonate) together with biological systems (citrate, transferrin) will be presented and discussed. The complexation between uranium and human transferrin has been pointed out through CIEF.