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Using in-situ Kelvin probe force microscopy (KPFM) to measure surface potential, we investigated the time-dependent work function evolution of solution-processed graphene oxide (GO) under ultraviolet (UV) irradiation. We found that the work function of GO exposed in UV shows a notable decrease with increasing irradiation time, which is proposed to be attributed to the gradual disappearance of oxygen-containing functional groups in GO during the UV-induced reduction reaction process. Fourier transform infrared spectrum and Raman spectrum were used to confirm the reduction of GO under UV irradiation. Our study would give an insight into understanding the transformation of GO’s electronic structures during the reduction process.