Novel Bi(V) complexes with the b-lactam antibiotics amoxicillin trihydrate (ACT) and ampicillin trihydrate (APT) ligands were prepared and studied by several spectral techniques both in solid as well in solution. The crystallographic data of the ligands and their relative complexes are given as a ¼ 13.9961 (A), b ¼ 5.1569(A) c ¼ 4.4571 (A) for ACT; a ¼ 21.45352 (A), b ¼ 21.45352 (A) c ¼ 4.57137, z ¼ 2 for Bi-ACT; a ¼ 19.051 (A), b ¼ 15.4799 (A) c ¼ 6.67522 (A) for APT; and a ¼ 22.24866 (A), b ¼ 4.254743 (A), c ¼ 12.08440 (A) for Bi-APT. The thermodynamic parameters DE*, DH*, DS*, DG* and K, were determined and have a good agreement with the X-ray powder diffraction data.