There have been considerable interests indinuclear, oligonuclear, and polynuclear cobalt complexes, because such units may be important as some cobalt-based magnetic materials having the anisotropic magnetic properties [1]. Dinucleating Schiff-base ligand, 1,3-bis(salicylideneamino)-2-propanol (H3salpr), and its substituted derivatives are good candidates for constructing such multinuclear cobalt species due to their dinuclear coordination sites [2-7]. In this study, we prepared mixed-valent cobalt species with a linear trinuclear CoIICoIII2 core by the reaction of H3salpr and its substituted analogues with cobalt salt. The isolated complexes were characterized by elemental analyses, IR and UV-Vis spectra, and single-crystal X-ray structure analysis, elucidating the chemical formula of [Co3(Hsalpr)2(CH3COO)4] as shown in Figure 1. We also isolated hexanuclear species with similar reactions. We report here the synthesis and crystal structures of these mixed-valent complexes.Figure 1. The crystal structure of [Co3(Hsalpr)2(CH3COO)4].