Artificial neural networks are used in various fields including spectral unmixing, which is used to determine the proportions of substances involved in a mixture, and achieve promising results. This is especially true if there is a non-linear relationship between the spectra of mixtures and the spectra of the substances involved (pure spectra). To achieve sufficient results, neural networks need lots of representative training data. We present a method that extends existing training data for spectral unmixing consisting of spectra of mixtures by learning the mixing characteristic using an artificial neural network. Spectral variability is considered by random inputs. The network structure used is a generative adversarial net that takes the dependence on the abundances of pure substances into account by an additional term in its objective function, which is minimized during training. After training further data for abundance vectors for which there is no real measurement data in the original training dataset can be generated. A neural network trained with the augmented training dataset shows better performance in spectral unmixing compared to being trained with the original dataset. The presented network structure improves already existing results obtained with a generative convolutional neural network, which is superior to model-based approaches.