Controlling charge doping in organic semiconductors represents one of the key challenges in organic electronics that needs to be solved in order to optimize charge transport in organic devices. Charge transfer or charge separation at the molecule/substrate interface can be used to dope the semiconductor (substrate) surface or the active molecular layers close to the interface, and this process is referred to as surface-transfer doping. By modifying the Au(111) substrate with self-assembled monolayers (SAMs) of aromatic thiols with strong electron-with drawing trifluoromethyl (CF3) functional groups, significant electron transfer from the active organic layers (copper(II) phthalocyanine; CuPc) to the underlying CF3-SAM near the interface is clearly observed by synchrotron photoemission spectroscopy. The electron transfer at the CuPc/CF3-SAM interface leads to an electron accumulation layer in CF3-SAM and a depletion layer in CuPc, thereby achieving p-type doping of the CuPc layers close to the interface. In contrast, methyl (CH3) -terminated SAMs do not display significant electron transfer behavior at the CuPc/ CH3-SAM interface, suggesting that these effects can be generalized to other organic-SAM interfaces. Angular-dependent near-edge X-ray absorption fine structure (NEXAFS) measurements reveal that CuPc molecules adopt a standing-up configuration on both SAMs, suggesting that interface charge transfer has a negligible effect on the molecular orientation of CuPc on various SAMs.