Materials exposed to extreme radiation environments such as fusion reactors or deep spaces accumulate substantial defect populations that alter their properties and subsequently the melting behavior. The quantitative characterization requires visualization with femtosecond temporal resolution on the atomic-scale length through measurements of the pair correlation function. Here, we demonstrate experimentally that electron diffraction at relativistic energies opens a new approach for studies of melting kinetics. Our measurements in radiation-damaged tungsten show that the tungsten target subjected to 10 displacements per atom of damage undergoes a melting transition below the melting temperature. Twoerature molecular dynamics simulations reveal the crucial role of defect clusters, particularly nanovoids, in driving the ultrafast melting process observed on the time scale of less than 10 ps. These results provide new atomic-level insights into the ultrafast melting processes of materials in extreme environments. © 2019 by the Authors.