An effective bottom-up technology for precisely controlling the amount of dopant atoms tethered on silicon substrates is presented. Polystyrene and poly-(methyl methacrylate) polymers with narrow molecular weight distribution and end-terminated with a P-containing moiety were synthesized with different molar mass. The polymers were spin coated and subsequently end-grafted onto nondeglazed silicon substrates. P atoms were bonded to the surface during the grafting reaction, and their surface density was set by the polymer molar mass, according to the self-limiting nature of the “grafting to” reaction. Polymeric material was removed by O2 plasma hashing without affecting the tethered P-containing moieties on the surface. Repeated cycles of polymer grafting followed by plasma hashing led to a cumulative increase, at constant steps, in the dose of P atoms grafted to the silicon surface. P injection in the silicon substrate was promoted and precisely controlled by high- temperature thermal treatments. Sheet resistance measurements demonstrated effective doping of silicon substrate. M. Perego et al. ACS Nano 2018, 12 178-186