A resist-free metallization of copper-plated contacts is attractive to replace screen-printed silver contacts and is demonstrated on large-area silicon heterojunction (SHJ) solar cells. In our approach, a self-passivated Al layer is used as a mask during the plating process. In this study, Al/AlOx or Al2O3 plating masks are further functionalized by a self-assembled monolayer (SAM) of octadecyl phosphonic acid (ODPA). The ODPA adsorption is characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy in attenuated total reflectance (FTIR-ATR) (in situ), and contact angle measurements to link the surface chemical composition to wetting properties. The SAM leads to homogeneous hydrophobic surfaces on large-area textured solar cells and planar flexible printed circuit boards (PCBs), which allows reproducible patterning of narrow lines by inkjet printing of an etchant. Selective copper plating is then performed to complete the metallization process and produce Cu contacts in the patterned areas. Silicon heterojunction (SHJ) solar cells metallized by the complete sequence reached up to 22.4% efficiency on a large area.