We report a deoxyribozyme (DNA enzyme) that catalyzes the convergent and general synthesis of branched DNA. The 15HA9 deoxyribozyme mediates nucleophilic attack of the 2'-hydroxyl group of a ribonucleotide embedded within one DNA substrate into a 5'-adenylate of the second DNA substrate. This approach can be used to synthesize multiply branched DNA with a wide range of DNA sequences.