Photoelectric charging is a very efficient way of charging small particles. This method can be applied to combustion measurement, electrostatic precipitator, metal separation and control of micro-contamination. To understand the photoelectric charging mechanism, particle charging of silver by exposure to ultraviolet is investigated in this study. Average charges and charge distributions are measured at various conditions, using two differential mobility analyzers, a condensation nucleus counter, and an aerosol electrometer. The silver particles are generated in a spark discharge aerosol generator. After that process, the generated particles are charged in the photoelectric charger using low-pressure mercury lamp that emits ultraviolet having wavelength 253.7 nm. The results show that ultra-fine particles are highly charged by the photoelectric charging. The average charges linearly increase with increasing particle size and the charge distribution change with particle size. These results are discussed by comparison with previous experiments and proposed equations. It is assumed that the coefficient of electron emission probability is affected by initial charge. The results also show that the charge distribution of a particle is dependent on initial charge. Single changed particle, uncharged particle and neutralized particle are compared. The differences of charge distribution in each case increase with increasing particle size.