The reaction of benzylferrocenyldithiophosphonate ligands [NH 4 ][S 2 P(OR)(Fc)] [R = Bz (1), 4-( i Pr)-Bz (2), 4-( t Bu)-Bz (3), 4-(Ph)-Bz (4), 3-(OBz)-Bz (5); Bz = benzyl, Fc = ferrocenyl] with organotellurium iodides, C 4 H 8 TeI 2 and C 8 H 8 TeI 2 , yielded the corresponding tellurium(IV) dithiophosphonate complexes [C 4 H 8 Te{S 2 P(OR)(Fc)} 2 ] [R = Bz (6), 4-( i Pr)-Bz (7), 4-( t Bu)-Bz (8), 4-(Ph)-Bz (9), 3-(OBz)-Bz (10)] and [C 8 H 8 Te{S 2 P(OR)(Fc)} 2 ] [R = Bz (11), 4-( i Pr)-Bz (12), 4-( t Bu)-Bz (13), 4-(Ph)-Bz (14), 3-(OBz)-Bz (15)]. Compounds 6–15 were characterized by elemental analyses, infrared, 1 H, 13 C, 31 P and 125 Te NMR spectroscopy and EI mass spectrometry, while complexes 6, 11 and 14 were also characterized by single-crystal X-ray diffraction studies. The dithiophosphonate ligands display an anisobidentate coordination mode upon interaction with the metal center. The solid-state structures show ferrocenyl groups in the dithiophosphonate ligands adopting trans arrangements.