Thirteen new bismuth(iii) dichalcogenone derivatives of triflates and halides were synthesized and structurally characterized. The mono, di, tetra and heptanuclear complexes were isolated with different bismuth(iii) coordination environments. These newly isolated bismuth(iii)dichalcogenones were characterized by multinuclear NMR, FT-IR, UV-vis, TGA and single crystal X-ray diffraction techniques. These complexes were tested for the synthesis of symmetrical triaryl- or triheteroarylmethanes and the catalysts were found to be highly active. In particular, the selone complexes were relatively more active than thione complexes. Subsequently, the scope of the catalytic reactions was further explored with different substituents. © The Royal Society of Chemistry 2016.