Spectral unmixing provides information on a sub-pixel level, which is extremely useful for studying the urban areas. Nevertheless, the high spatial diversity of man-made structures, the spectral variability of urban materials and the three-dimensional structure of the cities makes the sub-pixel mapping of urban surfaces one of the most challenging tasks of remote sensing science. In this study, these issues are addressed using an artificial neural network trained with endmember and non-linearly mixed synthetic spectra to inverse the pixel spectral mixture in high resolution multispectral imagery. A spectral library is built, consisting of endmember spectra collected from the images and synthetic spectra, produced using a non-linear model sp...