The regioselective hydrosilylation of terminal and internal alkynes catalyzed by the novel (IPr)Pt(AE) ( 7) (IPr = bis(2,6-diisopropylphenyl)imidazo-2-ylidene, AE = allyl ether) complex is presented. The (IPr)Pt(AE) catalyst displays enhanced activity and regioselectivity for the hydrosilylation of terminal and internal alkynes with low catalyst loading (0.1 to 0.05 mol %) when compared to the parent (IPr)Pt(DVDS) complex ( 6) (DVDS = divinyltetramethyldisiloxane). The reaction leads to exquisite regioselectivity in favor of the cis-addition product on the less hindered terminus of terminal and internal alkynes. The solvent effects were examined for the difficult hydrosilylation of benzylpropargyl ether. In light of the observed product distribution and kinetic data, a mechanistic scheme is proposed involving two competing catalytic cycles. One cycle leads to high regioselectivities while the other, having lost the stereodirecting IPr carbene ligand, displays low regiocontrol and activities. The importance of this secondary catalytic cycle is either caused by the strong coordinating ability of the alkyne or by the low reactivity of the silane or both.