The transition metal-free method for borylation of alkynes and alkenes with bis(pinacolato)diboron has been developed, producing the correspondent organoborons under mild reaction conditions. This reaction was an efficient, practical and environment-friendly process which brings forth vinylboronate products with excellent regioselectivity in the borylation of alkynes with bis(pinacolato)diboron, while in the meantime the diboryl alkanes were obtained using alkenes as substrates.