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To improve the accuracy of photovoltaic (PV) power prediction, this paper proposes a novel weather classification method. First, it distinguishs the clear days and cloudy days according to the total cloud cover. Then, it further classifies the cloudy days into three subtypes to investigate whether the sun is obscured by clouds. This method can effectively identify the characteristics of key meteorological environmental factors that affect PV output and form a new classification index sky condition factor (SCF) by weighted summation. This method has clear physical meanings, good discrimination, and easy quantification. The reasonable classification of weather types can eliminate the coupling relationship between many meteorological environmental factors and reduce the dimension of input variables, which makes it easy for statistical modeling. Based on the theoretical and the statistical approachs respectively, the modeling and verification are conducted and the results show that the method can effectively improve the accuracy of PV power prediction.