Chemical ligation has been investigated in the assembly of branched DNA (bDNA) molecules. Water soluble coupling reagents were used to ligate single-stranded linear oligomers to bDNA molecules containing 5 and 15 branches. The ligations were particularly efficient when one of the oligomers was partially double-stranded constructed by branching to create a terminal ligation linker (AutoLink). Branched DNA molecules containing more than 1000 nucleotides were assembled.