Allyltrimethylsilane (allyl-TMS) reacts with propargylic alcohols 1a–1d in the presence of 10% Bi(OTf)₃ in [BMIM][BF₄] solvent to furnish the corresponding 1,5-enynes in respectable isolated yields (87–93%) at room temperature. The utility of Bi(OTf)₃ as a superior catalyst was demonstrated in a survey study on coupling of allyl-TMS with 1a employing several metallic triflates (Bi, Ln, Al, Yb) as well as, B(C₆F₅)₃, Zn(NTf₂)₂ and Bi(NO₃)₃·5H₂O. Coupling of cyclopropyl substituted propargylic alcohol 1e with allyl-TMS gave the skeletally intact 1,5-enyne and a ring opened derivative as a mixture. Coupling of propargylic/allylic alcohol 1f with allyl-TMS resulted in allylation at both benzylic (2 isomers) and propargylic positions, as major and minor products respectively. The scope of this methodology for allylation of a series of allylic and benzylic alcohols was explored. Chemoselective reduction of a host of propargylic, propagylic/allylic, bis-allylic, allylic, and benzylic alcohols with Et₃SiH was achieved in high yields with short reaction times. The same approach was successfully applied to couple representative propargylic and allylic alcohols with 1-phenyl-2-trimethylsilylacetylene. The recovery and reuse of the ionic liquid (IL) was gauged in a case study with minimal decrease in isolated yields after six cycles.