▪ Abstract This review discusses the reactivities and thermodynamics of small-size-specific transition metal clusters and focuses on thermodynamic information, which has not been comprehensively discussed before. Because of this focus, guided-ion-beam mass spectrometry was used to acquire much of the data. The details of this technique and the associated data analysis methods are provided. Results on the stabilities of bare transition metal clusters are provided for neutral, cationic, and anionic species. Implications for the electronic and geometrical structures are discussed, as well as the extrapolation of these values to bulk phase behavior. Detailed results for reactions of transition metal clusters with D₂ and the oxygen donors O₂ and CO₂ are reviewed. Available bond energies between size-specific clusters and one D atom and one and two O atoms are compiled, and their implications are evaluated and favorably compared with bulk phase analogs. Several additional thermodynamic studies of various cluster systems are also discussed.