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Polar surfaces of a ferroelectric LiNbO3 crystal with periodically poled domains are explored using UV-photoelectron emission microscopy (PEEM). Compared with the positive domains (domains with positive surface polarization charges), a higher photoelectric yield is found from the negative domains (domains with negative surface polarization charges), indicating a lower photothreshold and a corresponding lower electron affinity. The photon-energy-dependent contrast in the PEEM images of the surfaces indicates that the photothreshold of the negative domains is ~4.6 eV while that of the positive domains is greater than ~6.2 eV. We propose that the threshold difference between the opposite domains can be attributed to a variation of the electron affinity due to opposite surface dipoles induced by surface adsorbates.