Although undoped diamond is insulating, hydrogenated bulk diamond surfaces exhibit surface conductivity under air and are electrochemically active in aqueous solutions. Due to their large surface/volume ratio, similar surface effects may exhibit a dramatic impact on the properties of nanodiamonds. Here we show that plasma-hydrogenated detonation nanodiamonds (NDs-H) display a positive zeta potential in water due to charge transfer with a redox couple involving oxygen in water. The transfer doping of NDs-H in water can be modulated by pH. Surprisingly, after acid addition, strong Coulomb coupling between NDs-H and adsorbed counterions induces the self-assembly of NDs-H into organized macro-structures reaching millimeter scale.