Element clustering and structural features of liquid lead-bismuth eutectic (LBE) alloy have been investigated up to 720 ffiC by means of high temperature X-ray diffraction (HT-XRD), X-ray Photoemission Spectroscopy (XPS) and Scanning Photoemission Microscopy (SPEM) at the Elettra synchrotron in Trieste. The short-range order in liquid metal after melting corresponds to the cuboctahedral atomic arrangement and progressively evolves towards the icosahedral one as temperature increases. Such process, that involve a negative expansion of the alloy, is mainly connected to the reduction of atom distance in Pb-Pb pairs which takes place from 350 ffiC to 520 ffiC. On an atomic scale, it is observed a change of the relative number of Bi-Bi, Pb-Pb, a...