Semiconductor doping through solution‐based self‐assembling provides a simple, scalable, and cost‐effective alternative to standard methods and additionally allows conformality on structured surfaces. Among the several solution‐based deposition techniques, dip coating is the most promising. It consists in immersing the target to be doped inside a solution containing the dopant precursor. During this process, the molecule bonds to the target surface with a self‐limiting process ruled by its steric properties. Successive annealing leads to layer decomposition and diffusion of dopant atoms inside the substrate. Most of the work on molecular doping lacks information on the molecule/Si interface chemical properties, on the mechanisms of the molecule evolution during the coating, and of its decomposition after the diffusion step. Moreover, it has so far been devoted to the molecules design to tune the final dopant dose …