C-C bond formation is one of the most fundamental approaches toward molecular diversity in organic synthesis. In pursuit of environmentally friendlier chemical approaches to organic chemistry, we present a new metal-free method for direct dehydrative cross-coupling of alcohols and alkenes using molecular iodine as a Lewis acid catalyst under solvent-free reaction conditions. The reaction is atom-economical, tolerant to air and allows simple synthetic procedure, furnishing C sp 3 -C sp 2 coupling products with yields up to 97 %. The method has proved efficient for coupling of secondary benzyl alcohols with phenyl-substituted alkenes.