We report here the efficient synthesis of 6,6´-diamido-2,2´-dipicolylamines (DA-DPAs) which could be applied to phosphate anion sensing via pre-formed metal complexes. The design was based on the retrosynthetic analysis. This strategy enabled us to achieve the functionalized DA-DPAs in satisfactory yields with high purity using the Boekelheide rearrangement. Meanwhile, all the intermediates could be easily purified by silica gel column chromatography.