The regioselectivity involved in the gas-phase hydride reduction of α,β-unsaturated carbonyl compounds by pentacoordinate silicon hydride ions is investigated. The kinetics and product distributions of the reactions of acrolein, methyl vinyl ketone and cyclohex-2-enone with monoalkoxysiliconate ions of the general composition RSiH3(OR′)− were examined with the flowing afterglow–triple quadrupole technique. All three substrates react by hydride transfer and by formation of a siliconate adduct in which hydride reduction of the organic reactant has occurred. The structures of these adducts and the hydride transfer products were identified by various tandem mass spectrometric protocols, including analysis of competitive collision-induced dissociation (CID) reactions and comparisons of CID spectra obtained from reference ions with known structures. 1,4-Reduction forming an enolate ion product is found to be the dominant or exclusive process with all three substrates, i.e. acrolein (70 ± 5%), methyl vinyl ketone (72 ± 5%) and cyclohex-2-enone (100%). Comparisons are made between these gas-phase results and the regioselectivity reported for analogous condensed-phase reactions. The observed behavior is discussed in terms of the reaction thermochemistry.