We observed the surface potential of silicon pn junctions using a Kelvin probe force microscope whose sensitivity was about five times better than that of a conventional one. It was achieved by three major improvements: electrostatic force detection using the second cantilever resonance, cantilever Q‐value enhancement by operating in a vacuum, and direct cantilever resonance frequency detection using the frequency modulation technique. It was demonstrated that the surface potential of the pn junctions made by thermal diffusion varies gradually compared to those made by ion implantation, possibly reflecting their gradual dopant concentration profile.