The coordination structure of cupric tartrate (Cu-TA) complex was investigated by ultraviolet-visible (UV-Vis) and liquid chromatography/mass spectrometer (LC-MS) firstly; furthermore, effective coordination configurations and electronic properties of Cu-TA in aqueous solution were systematically revealed by density functional theory (DFT) calculations. Consistently, Job plots show the possible existence of [Cu(TA)] and [Cu(TA)₂]^2- at 230 and 255 nm based on UV-Vis results. LC-MS results confirm the existence of the single and high coordination complexes [Cu₂(TA)₂]⁺, [Cu(TA)₂]⁺ and [Cu₂(TA)₃(H₂O)₂(OH)₂]²⁺. DFT calculation results show that carboxylic oxygen and hydroxyl oxygen of tartaric acid (TA) are preferred sites for Cu(II) coordination. [Cu(TA)] (1^H, 3^H sites O of TA coordinated with Cu(II)), [Cu(TA)₂]^2- (two 1^C, 2^H sites O of TA coordinated with Cu(II)), and [Cu(TA)₃]^4- (three 2^H, 3^H sites O of TA coordinated with Cu(II)) should be dominant coordination configurations of Cu-TA. The corresponding Gibbs reaction energies are -170.1, -136.2, and -90.2 kJ/mol, respectively.