Hot-filament chemical vapor deposition (HFCVD) was used to prepare boron-doped nanocrystalline diamond (BDND) nanoflowers on a Cu substrate with a Cu(OH)2 dendritic architecture that had been formed by using electrostatic self-assembly (ESA) method with nanodiamond particles. The formation of diamond nanoflowers is controlled by the reaction time between the Cu(OH)2 nanoflowers and the polymeric linker for the electrostatic attachment of nanodiamonds and by the deposition time for CVD diamond growth with a high nucleation density. Through analysis by field emission scanning electron microscopy (FESEM) and Raman spectroscopy, the optimal conditions for the synthesis of BDND nanoflowers are determined, and a possible explanation is provided.