The rate constants for the ozone reactions with n-butyl methyl sulfide (n-BMS, CH3CH2CH2CH2SCH3), sec-butyl methyl sulfide (s-BMS, CH3CH2(CH3)CHSCH3) and tert-butyl methyl sulfide (t-BMS, (CH3)3CSCH3) were measured using our smog chamber under supposedly pseudo-first-order conditions at 300±2 K and 760 Torr. The experimental determined rate constants for n-butyl, s-butyl and t-butyl methyl sulfide are (1.23 ± 0.06)×10−19, (5.08 ± 0.19)×10−20 and (2.26 ± 0.14)×10−20 cm3·molecule−1·s−1, respectively. The reactivity-structure relationship of the reactions was discussed and used to illustrate the mechanism of the ozone reaction with thioethers. The results enrich the kinetics data of atmospheric chemistry.