The temperature-dependent reaction properties of actinide elements are of particular interest in the safety assessment of high-level radioactive waste (HLRW) disposal systems. In this study, the hydrolysis of Pu(III) and the solubility of Pu(OH)3(am) were investigated at various temperatures (10-40 °C) in 0.1 M NaClO4. A strong reducing condition for maintaining the oxidation state of Pu(III) while slowly increasing the pH of the solution was realized by electrolysis. The formation constants of the first hydrolysis species, log *β1', and the solubility products of Pu(OH)3(am), log *Ks,0', at 10, 17, and 40 °C were experimentally determined using spectrophotometry, laser-induced breakdown detection, and radiometry. The enthalpy and entropy changes for these reactions were estimated using the van't Hoff equation. The first hydrolysis of Pu(III) is endothermic (ΔrHm° = 34.10 ± 4.48 kJ mol-1), and the dissolution of Pu(OH)3(am) is exothermic (ΔrHm° = -294.29 ± 23.05 kJ mol-1) with negative entropy changes. These thermodynamic data will contribute to improving the reliability of the safety assessment of HLRW disposal facilities and understanding the geochemical behavior of Pu under reducing or anoxic aqueous conditions at elevated temperatures.