We confirmed methyl termination on n-Si(111) surface by ATR-FTIR measurement, which was fabricated by a photo chloro-reaction and its methylation. The coverage of the methylation was about 63.7%, and the surface was not re-terminated by hydrogen. Photoelectrochemical properties of the n-Si(111) were measured as an electrode for a photoelectrochemical cell, and an onset potential obtaining photocurrent for the methyl terminated n-Si(111) electrode was observed as negative shift at 70 mV comparing with that of the hydrogen terminated n-Si(111) electrode. Therefore, the negative shift would be expected for improving open circuit voltage towards solar cell.