The synthesis, structural characterization, and NMR studies of new tin(II) alkoxides with thiophene-based substituents are presented. The reaction of ligand HO-C(C
4
H
3
S)
3
(
1
) with bis(hexamethyldisilazyl)tin {Sn[N(SiMe
3
)
2
]
2
} in the ratio 2:1 in toluene yields the dinuclear compound {Sn[OC(C
4
H
3
S)
3
]
2
}
2
∙ 2 toluene (
2
). The same reaction in tetrahydrofuran allows the isolation of two compounds: a dinuclear {Sn[OC(C
4
H
3
S)
3
]
2
}
2
∙ 2 thf (
3
) and a mononuclear Sn[OC(C
4
H
3
S)
3
]
2
(thf) (
4
) molecule. The molecular structures of these tin(II) methoxides containing thienyl substituents
2-4
were investigated by single-crystal X-ray crystallography. The NMR spectra of solutions of Sn[OC(C
4
H
3
S)
3
]
2
}
2
∙ 2 toluene (
2
) or {Sn[OC(C
4
H
3
S)
3
]
2
}
2
∙ 2 thf (
3
) and {Sn[OC(C
4
H
3
S)
3
]
2
}
2
(thf) (
4
) are almost identical, showing only variations of the molar ratio of the dimeric and monomeric compounds.