Ultrafast excited-state dynamics of CuBr₃^-complex was studied in acetonitrile and dichloromethane solutions using femtosecond transient absorption spectroscopy with 18 fs temporal resolution and quantum-chemical DFT calculations. Upon 640 nm excitation, the CuBr₃^-complex is promoted to the ligand-to-metal charge transfer (LMCT) state, which then shortly undergoes internal conversion into the vibrationally hot ligand field (LF) excited state with time constants of 30 and 40 fs in acetonitrile and dichloromethane, respectively. The LF state nonradiatively relaxes into the ground state in 2.6 and 7.3 ps in acetonitrile and dichloromethane, respectively. Internal conversion of the LF state is accompanied by vibrational relaxation that occurs on the same time scale. Based on the analysis of coherent oscillations and quantum-chemical calculations, the predominant forms of the CuBr₃^-complex in acetonitrile and dichloromethane solutions were revealed. In acetonitrile, the CuBr₃^-complex exists as [CuBr₃(CH₃CN)₂]⁻, whereas three forms of this complex, [CuBr₃CH₂Cl₂]⁻, [CuBr₃(CH₂Cl₂)₂]⁻, and [CuBr₃(CH₂Cl₂)₃]⁻, are present in equilibrium in dichloromethane.