Catalytic intramolecular hydrofunctionalizations of acyclic alkenes and alkynes are desired methods for the construction of pharmaceutically important heterocycles with 100% atom efficiencies. Although electrophilic activation of alkenes and alkynes in the presence of Lewis basic hydroxy and amino groups can cause the reactions, those of monoalkyl- and 1,2-dialkyl-substituted alkenes and alkynes called unactivated alkenes and alkynes are difficult owing to their inherent reactivity. Herein, we introduce several transition metal-free novel catalytic systems for the intramolecular hydrofunctionalization of such unactivated alkenes and alkynes; iodine-silane catalytic system for the hydroalkoxylation of unactivated alkenes, Brønsted acid-silane and iodine-silane catalytic systems for the hydrofunctionalization/reduction of unactivated alkynes, and boron catalytic systems for double hydrofunctionalization reactions of unactivated alkynes. A novel active species, iodophenylsilane (PhSiH₂I) efficiently catalyzes the intramolecular hydroalkoxylation of unactivated alkenes in the iodine-silane catalytic system. A super strong Brønsted acid catalyst can activate unactivated alkynes in the presence of silane to cause the hydrofunctionalization/reduction. Tris(pentafluorophenyl)borane [B(C₆F₅)₃] chemoselectively activates unactivated alkynes in the presence of allylsilane to cause the intramolecular hydrofunctionalization/hydro-allylation. In addition, tris(pentafluorophenyl)borane hydrate [B(C₆F₅)₃·nH₂O] reacts with trime-thylsilylcyanide to form H⁺[NCB(C₆F₅)₃]^-, which catalyzes the intramolecular hydroalkoxylation/hydrocyanation of unactivated alkynes. These catalytic methods enable the rapid construction of multiply-substituted oxygen-or nitrogen-containing heterocycles.