The thermochemical properties of alloys were determined for the first time by calorimetry Bi—Eu system at a temperature of 1200 K in the range of 0 ≤ xBi ≤ 0,2 and 0,77 ≤ xBi ≤ 1,0. It is established that the minimum value of the enthalpy of mixing is equal to –61,7 ± 0,5 kJ / mol at xBi = 0,5. = –184,7 ± 16,7 kJ / mol, = = –206,9 ± 21,8 kJ / mol. The activities of the components were calculated according to the model of an of the ideal associated solution (IAR), using the thermochemical properties of the melts of the Bі—Eu. system. It has been established that the activities of the components show large negative deviations from ideal solutions. To predict the enthalpies of formation of LnBi compounds, the available literature data on these parameters are analyzed and the most reliable ones are presented as a dependence on ∆fH = f(ZLn). It is established that the enthalpies of formation LnBi change smoothly and monotonically with the exception of Bi—Eu and Bi—Yb systems. This is due to the large size factors for the last two systems. To combine all the enthalpy data of Ln—Bi intermetallic formation of Ln—Bi systems depending on the sequence number Ln, we need similar values for the Eu—Bi compound. But at present they are not known, so based on the above, it was assumed that the value of the minimum enthalpy of mixing will be close to the enthalpy of formation of this compound. This hypothesis is confirmed by data on the enthalpies formation of phase YbBi and equiatomic melts of binary of Yb—Bi system. To confirm the thermodynamic data, we compare the known melting temperatures of the formed intermediate phases, known from the diagrams state Bi—Ln system. The obtained dependences correlate with ∆fH = f(ZLn ) і ∆V = f(ZLn). This means that the predictions of thermochemical properties accurately reflect the nature of the considered melts of the Bi—Eu system. Keywords: thermochemical properties, melts, compounds, Bi, Eu.