This work provides direct access to the complex [Tb(hfa)3(H2O)2] with elucidation of the molecular and crystal structure. It has been shown that the interaction of Tb(OAc)3 ⋅ 4H2O with H-hfa ⋅ 2H2O in water gives {[Tb2(hfa)4(F3CCO2)2(H2O)4][Tb(hfa)3(H2O)2]2 ⋅ H2O}, which can be used as a source of pure [Tb(hfa)3(H2O)2]. This compound is a good quantitative precursor for the synthesis of various Tb(hfa)3 complexes due to its good solubility in common organic solvents such as hexane, benzene, ether and acetone. Hence, it opens new possibilities in the field of molecular magnetism and design for photonic and optoelectronic applications.