Digital sky images are studied for the definition of sky conditions in accordance with the CIE Standard General Sky Guide. Likewise, adequate image-processing methods are analyzed that highlight key image information, prior to the application of Artificial Neural Network classification algorithms. Twenty-two image-processing methods are reviewed and applied to a broad and unbiased dataset of 1500 sky images recorded in Burgos, Spain, over an extensive experimental campaign. The dataset comprises one hundred images of each CIE standard sky type, previously classified from simultaneous sky scanner data. Color spaces, spectral features, and texture filters image-processing methods are applied. While the use of the traditional RGB color space for image-processing yielded good results (ANN accuracy equal to 86.6%), other color spaces, such as Hue Saturation Value (HSV), which may be more appropriate, increased the accuracy of their global classifications. The use of either the green or the blue monochromatic channels improved sky classification, both for the fifteen CIE standard sky types and for simpler classification into clear, partial, and overcast conditions. The main conclusion was that specific image-processing methods could improve ANN-algorithm accuracy, depending on the image information required for the classification problem.