Bismuth oxide, an inexpensive and non-toxic semiconductor, has been successfully used as a visible light photocatalyst for
the atom transfer radical addition (ATRA) reaction of organobromides to diversely functionalized terminal olefins. The reaction takes place under very mild conditions, in the absence of any additive, and with low catalyst loading (1 mol%). The corresponding ATRA products are obtained with moderate to excellent yields (up to 95 %).