Three new bimetallic complexes are synthesized and crystalized by reactions of (CF 3 CO 2 ) 2 Ln with R 1 AlR 2 (Ln = Nd and Y, R 1 = H, R = i-C 4 H 9 ; Ln = Eu, R = R 1 = C 2 H 5 ) in tetrahydrofuran solution, and their crystal structures are determined using a X-ray diffraction method. The structures and the questions on valence state and noncoplanarity in the structures are confirmed and cracked by means of 1 HNMR and 1 2 CNMR spectra, especially by 1 3 C- 1 H cosy 2D NMR technique. A general formula of molecules of the three rare earth complexes is defined as follows: [(μ-CF 3 CO 2 ) 2 Ln (μ-CF 3 CHO 2 )AlR 2 . 2THF] 2 .