AbstractMass spectra of trimethylsilyl esters of nine specifically deuterated decanoic acids and of trimethylsilyl ethers of the corresponding deuterated decanols and of tri[2H3] methylsilyl derivatives of most of the acids and of decanol have been measured. The fragmentation patterns have been used to examine the formation of ions m/z 117, 129, 131, 132, 145, 159, 171, 185 and 201 in the spectrum of the TMS ester of decanoic acid. Mechanisms of breakdown of one ion to another have been proposed. Similarities and differences in ion formation between spectra of TMS esters and methyl esters have been examined. It has been shown that ion m/z 132 is produced by the McLafferty rearrangement and that ion m/z 117 is formed from it by loss of a silyl methyl group. Ion m/z 145 is formed by hydrogen transfer from C‐5, C‐6 or C‐7 to the carbonyl oxygen and γ‐cleavage. Ion m/z 129 is formed from ion m/z 145 by loss of the previously transferred hydrogen and a silyl methyl group. A mechanism of formation of ions m/z 115, 129, 143 and 157, which contained only one silyl methyl group, observed in the mass spectrum of the TMS ether of decanol, has been proposed. Ions in spectra of the derivatives can be used to locate the position of deuterium, or other substituents, at a number of the carbons of decanoic acid or decanol.