The release behavior of radioactive materials from high active liquid waste (HALW) has been investigated under boiling accident conditions. Results of the experiment using a nonradioactive simulated HALW found Ru to be a volatile element under the accident conditions and to be released into the gas phase in the form of both mist and gas. The Ru release rate and the apparent Ru volatilization rate constant were obtained under the boiling conditions of simulated HALW. The other fission product elements such as Cs were found to be nonvolatile and to be released into the gas phase in the form of mist. The mist size distribution near the surface of the simulated HALW in the reactor vessel was found to range from 0.05 to 20 μm with a peak diameter of ∼2 μm.