Three types of metal ions barium(Ⅱ), nickel(Ⅱ) and cerium(Ⅲ) complexity of ATN drug have been prepared and characterized using molar conductance method, FT-IR, electronic, and 1H-NMR analysis measurements. The chemical and physical results for all atenolol complexes are agreement with the speculated structures. For the divalent (Ba & Ni) and trivalent (Ce) metal atenolol a molar ratio 1∶2 was established. Qualitative chemical analysis showed that for the divalent metal complexes, the chloride ions are not involved in the complexes, suggesting that all of these complexes, ［Ba(ATN)2］·2H2O and ［Ni(ATN)2(H2O)2］·4H2O are neutral. However, for the cerium(Ⅲ) complex, ［Ce(ATN)2(NO3)］·3H2O, the nitrate group is existed inside the coordination sphere. ATN make astable metal complexity with barium(Ⅱ), nickel(Ⅱ) and cerium(Ⅲ) ions. Electronic absorption analysis of Atenolol give two fundamental peaks at 225 nm and 274 nm refers to variation in transition electrons of ligand, UV spectral analysis of the three complexity obtained give asymmetric broad band in the range 200～400 nm, the reults are convenient with the suggestion of metal-nitrogen and metal -oxygen bonds. The infrared analysis data proved that ATN act as bidentate ligand through the N atom of the -NH group and O atom of the deprotonated alcoholic OH group. Nickel(Ⅱ) and cerium(Ⅲ) complexity make six-coordinate geometry, whereas the barium(Ⅱ) complex exhibit four-coordinate geometry. Ni(Ⅱ)-ATN complex has an effective magnetic moment equal 3.12 B.M, that is assigned to octahedral structure. The 1H-NMR spectral results of Ba(Ⅱ)-ATN complexity give strong signal at ~4.00 ppm due to protons of -CH2 that influenced by low degree due to complexity. These results confirm the position of chelation through the N atom of the -NH group and O atom of the deprotonated alcoholic OH group.