[reaction: see text] A novel catalytic system of AgOTs-CuCl(2)-TMEDA is described for the homocoupling of aliphatic acetylenes on solid support. It is the first observation that Ag(I)'s activating triple bond could facilitate Cu(II)-mediated oxidative acetylenic homocoupling. This study provides an efficient way to synthesize a diversified symmetrical bis-benzo[b]furan-linked 1,3-diyne library on solid support.