A detailed study of the solution chemistry and mass spectrometry of six carboxylato‐organogermanium compounds in aqueous solution has been carried out using electrospray ionization and MSn techniques. The different types of hydrolysis products and their probable structures, which include the oligomers and their fragment ions plus water adduct ions formed by ion‐molecule reactions, are presented, e.g., HO‐cyclic‐(‐Ge(O−)CH2CH2COO) A, HO‐cyclic‐(‐Ge(O‐cyclic‐(Ge(O−)CH2CH2COO)CH2CH2COO) B, −OGeO‐cyclic‐(‐Ge(OH)CH2CH2COO) C, and −CH=CHGeO‐cyclic‐(‐Ge(OH)CH2CH2COO) D, etc. The proposed cyclic structures are confirmed by theoretical calculations. Copyright © 2001 John Wiley & Sons, Ltd.