Three unknown olivacine derivatives (L‐OCH3, L‐OH, L‐OAc) were synthesized according to a procedure that involves only a few steps, and used as ligands in the synthesis of neutral chelate platinum(II) complexes. The ligands, as well as their platinum complexes were spectroscopically characterized with IR, 1H/13C NMR and UV/Vis spectroscopic techniques. The solid state structures of two ligands (L‐OCH3, L‐OAc) and one complex {[(L‐OCH3)PtCl2]} were determined by X‐ray diffraction. Molecular structure analysis of the ligands and the complex indicated that complexation resulted in a change in the conformation of the bipyridine fragment of the compounds studied and caused other interesting effects. Two crystallographically independent molecules of the complex were revealed in the measured crystal, with short intramolecular H···H distances. The structural and energetic aspects of the conformational behavior of the ligand L‐OCH3 and the complex [(L‐OCH3)PtCl2] have been analyzed using semiempirical PM3 methods. In vitro antiproliferative activity was preliminarily estimated. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)