Dendritic macromolecules with 8 and 16 hydroxy end-groups on the periphery have been synthesized using double click reactions (Cu-catalyzed azide/alkyne click chemistry, i.e., CuAAC and Diels–Alder [4 + 2] cycloaddition reactions) with a one-pot technique. The structure of the dendrimers was characterized by ¹H and ¹³C NMR spectroscopy, and matrix-assisted laser desorpton–ionization time-of-flight mass spectrometry. The purity was determined by size exclusion chromatography.