A new tripodal C-anionic ligand, 2-{bis(benzothiazolyl)(methoxy)methyl}phenyl (L), was stably generated by the reaction of the ligand precursor (L'), the corresponding bromide (2-BrC6H4)(MeO)C(C7H4NS)2 (C7H4NS = 2-benzothiazolyl), with nBuLi at -104 °C in the presence of TMEDA (N,N,N',N'-tetramethylethylenediamine). The ligand lithium salt reacted with BiCl3 to give a 2 : 1 complex L2BiCl. A 1 : 1 complex LBiCl2 was obtained in good yield by the redistribution reaction between L2BiCl and BiCl3. X-ray diffraction analysis revealed that the ligand L coordinated in an expected κ3-C,N,N' coordination mode in LBiCl2, while it coordinated in κ3-C,N,O and κ2-C,O coordination modes in L2BiCl. The ligand precursor reacted with BiX3 (X = Cl, Br) to give 1 : 1 complexes L'BiX3 and was found to act as a neutral tripodal C(π),N,N-ligand.