Bimuth(III) complexes with 1,4,7,10-tetrakis(2-pyridylmethyl)-1,4,7,10-tetraazacyclododecane have been prepared in dichloromethane and ethanol and investigated. These complexes have been characterized structurally by X-ray diffraction and NMR-2D studies. They present different coordination scheme depending on the reaction conditions: according to the nature of solvent, bismuth coordinates from six to eight nitrogen atoms and forms in the solid state a chiral structure which is maintained in solution.