We demonstrate that the hexadehydro-Diels-Alder (HDDA) cycloisomerization reaction to produce reactive benzyne derivatives can be initiated photochemically. As with the thermal variant of the HDDA process, the reactive intermediates are formed in the absence of reagents or the resulting byproducts required for the generation of benzynes by traditional methods. This photo-HDDA (or h nu-HDDA) reaction occurs at much lower temperatures (including even at -70 degrees C) than the thermal HDDA, but the benzynes produced behave in the same fashion with respect to their trapping reactions, suggesting they are of the same electronic state.