On the basis of measuring the electrical resistivity of Sn melt and referring to analysis of high temperature XRD, the change of electrical resistivity and structure for Sn melt with temperature was carried out. The results show that there is discontinuous change of electrical resistivity for Sn melt with the temperature in the metrical temperature range. There is a correlation between the electrical resistivity change and the structure change of Sn melt. The correlation radius and the fluid cluster size of Sn melt decrease with the increasing of temperature, so that the electrical resistivity of Sn melt increases. But there is an anomalous change in the vicinity 673K, it results in a discontinuous change in electrical resistivity of Sn melt.