Abstractmagnified imagePeptides and oligodeoxynucleotides containing photolabile 2‐nitrobenzyl groups as mid‐sequences were prepared. Photocleavage of aqueous solutions of these compounds neared completion within 30 min to a few hours depending on the photolabile group used. A photolabile group was introduced in the loop of an intramolecular oligodeoxynucleotide hairpin. Melting curves of the hairpin with and without the complementary oligodeoxynucleotide showed a preference for the intramolecular hairpin form, but an intermolecular duplex was observed after photolysis. These results open the possibility of using photolabile DNA hairpins for the fabrication of patterned surfaces.