First manganese(II) trialkoxysilanethiolates have been prepared using tri-tert-butoxysilanethiol as the ligand source and their structure determined by X-ray diffraction. Acetonitrile or methanol used as reaction solvents was found to enter Mn coordination sphere. Obtained heteroleptic silanethiolate complexes represent two distinct structural types. Either O,S-chelation by tri-tert-butoxysilanethiolate ligand and simultaneous electronic assistance provided by acetonitrile in [Mn{SSi(OBu t ) 3 } 2 (MeCN)] or formation of four intramolecular, interligand O–H ⋯ O hydrogen bonds in the case of [Mn{SSi(OBu t ) 3 } 2 (MeOH) 4 ] serve to stabilize the complexes.