Homopolycouplings of aryltriynes Ar(Cequivalent toCH)(3) and their copolycouplings with monoyne Ar'Cequivalent toCH are effected by CuCl in air under Glaser-Hay oxidative coupling conditions, giving soluble hyperbranched polyynes (hb-PYs). Hyperbranched poly[tris(4-ethynylphenyl)amine] emits bright blue light (lambda = 440 nm) and shows high light refractivity (n = 1.770-1.861). Its peripheral terminal triple bonds can be 100% end-capped by aromatic rings via palladium-catalyzed coupling with aryliodides. The carbon-rich polyynes are readily curable (from similar to150 degreesC), thermally stable (T-d up to -550 degreesC), and pyrolytically carbonizable (W-r up to similar to80% at 900 degreesC). Complexations with cobalt carbonyls metallify the hb-PYs, and ceramizations of the cobalt-polyyne complexes afford soft ferromagnetic materials with high magnetizability (M-s up to similar to118 emu/g) and low coercivity (H-c down to similar to0.045 kOe).