Abstract Di-t-butyltin oxide (t-Bu 2 SnO) 3 and di-t-amyltin oxide (t-Am 2 SnO) 3 were synthesized by hydrolysis of the diorganotin dichlorides. Their molecular and crystal structures were investigated by X-ray diffraction techniques and vibrational spectroscopy. Both compounds form isolated molecules with planar six-membered tin-oxygen rings.