A widely used approach to obtain smooth oxide-free and (partially) H-terminated silicon (Si) surfaces is to immerse Si wafers into CP4A (a mixture of H2O, HNO3, CN3COOH and HF in a volume ratio of 22:5:3:3) and/or HF solutions of varying concentrations. It is usually assumed that such treatments result in a dramatic reduction of the surface density of states and that, therefore, no surface band bending can occur. In our experiments we investigated the electronic surface structure of a number of CP4A/HF treated n- and p-Si wafers with varying doping densities by x-ray photoelectron spectroscopy (XPS). XPS allows a straightforward detection of surface stoichiometry as well as one of band bending and surface photovoltages (SPV) on semiconductor materials because the positions of the core level peaks directly depend on the position of the Fermi level within the band gap at the surface. Our experiments show that on all surfaces investigated Fermi level pinning still exists after the samples were immersed in the CP4A/HF solutions and that the pinning states are located close to the conduction band. Most of the samples also showed SPV when measured under illumination. The measurements also show that up to 36.6% of the surfaces are covered by F atoms depending on the treatment and the doping density. From the amount of blind bending we estimated the density of surface states present on the various samples.