The crystal structure of the title compound, [Co3(C5H9O2)6O(CH4O)3]Cl, consists of trinuclear CoIII complex cations and chloride anions. The CoIII cation has site symmetry m, and is coordinated by four oxygen atoms from four bridging pivalate groups, one central O anion and a methanol oxygen atom, forming a distorted octahedral geometry. The coordinated methanol molecule is located on a crystallographic special position, the C and O atoms being located on the mirror plane. The central O anion lies in the crystallographic overline6 position, and acts as a μ3-O bridge, linking three equivalent CoIII cations and generating the oxo-centered trinuclear CoIII complex. The chloride anion, which acts as the counter-ion, is located on crystallographic overline6 position. O—H...Cl hydrogen bonding between the Cl anion and hydroxyl group of the coordinated methanol molecule links the molecules into a supramolecular network.