The relation between annealing temperature and surface photovoltage (SPV) shifts on the Si(111)7×7 surface of lightly n-doped substrates has been studied by core-level and valence-band photoelectron spectroscopies at 100 K. The SPV shift was found to depend strongly on the annealing temperature and the photon flux. Between 900 and 1150 °C the magnitude of the SPV shift shows a general decrease with annealing temperature. After a narrow plateau, the SPV shift becomes positive for annealings at 1250 and 1270 °C. As a consequence, the adatom surface state of the 7×7 surface appears above the Fermi level. The unexpected SPV shift can be explained by the formation of a p-type layer during high-temperature annealing of the Si sample. The role of boron and carbon contaminations has been discussed in this context in the literature. By correlating the SPV shifts with the C 1s and B 1s core-level signals, we conclude that carbon, but not boron, is involved in the formation of the p-type layer. Further, our results show that the annealing temperature plays a crucial role when binding energies are determined from photoemission spectra at low temperature. The effect is of particular importance in the study of surface band-gap openings related to phase transitions at low temperature.