A transition-metal-free coupling of triorganoindium reagents with benzopyranyl acetals mediated by a Lewis acid has been developed. The reaction of R3In with chromene and isochroman acetals in the presence of BF3·OEt2 afforded 2-substituted chromenes and 1-substituted isochromans, respectively, in good yields. The reactions proceed with a variety of triorganoindium reagents (aryl, heteroaryl, alkynyl, alkenyl, alkyl) using only 50 mol % of the organometallic, thus demonstrating the efficiency of these species. Preliminary mechanistic studies indicate the formation of an oxocarbenium ion intermediate in the presence of the Lewis acid.