Silicon nanowires (SiNWs) combined with a conducting polymer are studied to constitute a hybrid organic/inorganic solar cell. This type of cell shows a particularly high interfacial area between SiNWs and the polymer so that interfacial control and interface optimization are required. For that purpose, we terminated the SiNW surfaces with well selected functional groups (molecules) such as native oxide (hereinafter SiO2-SiNW), hydrogen (hereinafter H-SiNW) and methyl (hereinafter CH3-SiNW). A radial hetero-junction solar cell is formed, and the cell parameters with and without interface control by functionalization with molecules are compared. Electronically, the three surfaces were close to flat-band conditions. The CH3-SiNW, H-SiNW and SiO2-SiNW produced a surface dipole of −0.12, +0.07 and 0.2 eV and band bending of 50, 100 and 170 meV, respectively. The surface properties of functionalized SiNWs are investigated by photoelectron yield (PY) and photoemission spectroscopy. PY studies on functionalized SiNWs are presented for the first time, and our results show that this type of measurement is an excellent option to carry out interface optimization of NWs for envisaged nano-electronic and photonic applications. The solar cell efficiency is increased dramatically after terminating the surface with CH3 molecules due to the decrease of the defect emission. The differently functionalized SiNW surfaces showed identical absorbance, reflectance and transmission so that a change in PY can be attributed to the Si–C bonds at the surface. This finding permits the design of new solar cell concepts. Copyright © 2013 John Wiley & Sons, Ltd.