For the safety assessment of the high-level radioactive waste (HLRW) disposal, the thermodynamic data such as solubility products, formation constants of complexes, redox equilibrium constants of radionuclides, and their reaction enthalpy and entropy are required. In order to recommend and summarize the reliable data, thermodynamic databases (TDB) have been persistently developed through the OECD-NEA TDB projects and an updated TDB of actinides has been recently published in 2020. To date, reliable data for Pu reactions are scarce due to the possibility of coexistence of four different oxidation states, Pu(III-VI) by redox equilibria in solutions. To determine the thermodynamic data for the reaction of each Pu oxidation state, it is necessary to precisely control the oxidation state and quantitatively analyze all reactants, products and bi-products by using highly sensitive speciation techniques. Since 2004, the nuclear chemistry research team in KAERI has been focused on developing techniques for the sensitive chemical speciation by using laser-based spectroscopy and determining thermodynamic data of actinides such as U, Pu, Am. In this paper, chemical speciation and thermodynamic studies on Pu in KAERI are reviewed. A combination of a commercial spectrophotometer and a capillary cell was adopted for a sensitive chemical speciation of Pu(III-VI) in solutions. A sensitive detection of trace amount of Pu colloids was carried out with the laser-induced breakdown detection (LIBD) system. Pu(VI) complexation with hydroxide or carbonate ions were investigated under strong oxidation conditions controlled with hypochlorite (NaOCl). The solubility product of Pu(OH)3(am) and formation constant of Pu(III)-OH speices were determined by a combination of wet-chemistry experiments and several analysis methods of spectrophotometry, LIBD, radiometry under a strong reducing condition controlled by electrochemistry. More recently, we reported the reaction enthalpy and entropy data for the formation of Pu(OH)2+ and the dissolution of Pu(OH)3(am). A preliminary data for reaction between Pu(III) and organic matter will be presented.