The conditions of the formation of Co(II), Ni(II), Cu(II) and Zn(II) benzene-1,3-dioxyacetates were studied and their quantitative composition and solubilities in water at 293 K were determined. The IR spectra and X-ray diffractograms were recorded and their thermal decompositions in air were investigated. During heating, the hydrated complexes MC10H8O6.nH2O lose some crystallization water molecules in one or two steps, then decompose to the oxides directly (Zn and Cu) or with intermediate formation of the free metals (Co, Ni).