Trialkyltin n-$Bu_3SnH$, an endocrine disruptor, was slowly converted by the catalytic action of group 4 $Cp_2MCl_2$/Red-Al (M = Ti, Zr, Hf) to produce two phases of products: one is an insoluble cross-linked solid, polystannane in 7-23% yield as minor product via redistribution/dehydrocoupling combination process, and the other is an oil, hexabutyldistannane in 69-90% yield as major product via simple dehydrocoupling process. Redistribution/dehydrocoupling process first produced a low-molecular-weight oligostannane possessing partial backbone Sn-H bonds which then underwent an extensive cross-linking reaction of backbone Sn-H bonds, leading to an insoluble polystannane. This is the first exciting example of redistribution/dehydrocoupling of a tertiary hydrostannane catalyzed by early transition metallocenes.