A series of silicon‐containing derivatives of the polycyclic musk odorant galaxolide (4 a) was synthesized, that is, disila‐galaxolide ((4RS,7SR)‐4 b/(4RS,7RS)‐4 b), its methylene derivative rac‐9, and its nor analogue rac‐10. The tricyclic title compounds with their 7,8‐dihydro‐6,8‐disila‐6 H‐cyclopentagisochromane skeleton were prepared in multistep syntheses by using a cobalt‐catalyzed 2+2+2 cycloaddition of the mono‐ yne H2CCHCH2OCH2CCB(pin) (B(pin)=4,4,5,5‐tetramethyl‐1,3,2‐di‐ oxaborolan‐2‐yl) with the diynes H2CCSi(CH3)2CCH2 or H2C‐ Si(CH3)2CCH2 as the key step. Employing Cr(CO)3(MeCN)3 as an auxiliary, the disila‐galaxolide diastereomers (4RS,7SR)‐4 b and (4RS,7RS)‐4 b could be chromatographically separated through their tricarbonylchromium(0) complexes, followed by oxidative decomplexation. The identity of the title compounds and their precursors was established by elemental analyses and multinuclear NMR spectroscopic studies and in some cases additionally by crystal structure analyses. Compounds (4RS,7SR)‐4 b, (4RS,7RS)‐4 b, rac‐9, and rac‐10 were characterized for their olfactory properties, including GC‐olfactory studies of the racemic compounds on a chiral stationary phase. As for the parent galaxolide stereoisomers 4 a, only one enantiomer of the silicon compounds (4RS,7SR)‐4 b, (4RS,7RS)‐4 b, rac‐9, and rac‐10, smelt upon enantioselective GC‐olfactometry, which according to the elution sequence is assumed to be also (4S)‐configured as in the case of the galaxolide stereoisomers. The disila‐analogues (4S,7R)‐4 b and (4S,7S)‐4 b were, however, about one order of magnitude less intense in terms of their odor threshold than their parent carbon compounds (4S,7R)‐4 a and (4S,7S)‐4 a. The introduction of a 7‐methylene group in disila‐galaxolide (4 b→rac‐9) improved the odor threshold by a factor of two. With the novel silicon‐containing galaxolide derivatives, the presumed hydrophobic bulk binding pocket of the corresponding musk receptor(s) could be characterized in more detail, which could be useful for the design of novel musk odorants with an improved environmental profile. Fragrant sila‐musks: Silicon‐containing derivatives of the polycyclic musk odorant galaxolide (see scheme) were synthesized and characterized for their olfactory properties. The disila‐galaxolide diastereomers (4RS,7SR) and (4RS,7RS) were obtained by chromatographic separation of their corresponding chromium complexes, followed by oxidative decomplexation. The relatively rigid structures of these polycycles, in combination with the carbon/silicon switch strategy, makes the single stereoisomers of these C/Si analogues ideal candidates for structure–odor correlations in the musk domain.