Multiple Endmember Spectral Mixture Analysis (MESMA) is one of the leading approaches to perform spectral unmixing (SU) considering variability of the endmembers (EMs). It represents each endmember in the image using libraries of spectral signatures acquired a priori. However, existing spectral libraries are often small and unable to properly capture the variability of each endmember in practical scenes, what significantly compromises the performance of MESMA. In this paper, we propose a library augmentation strategy to improve the diversity of existing spectral libraries, thus improving their ability to represent the materials in real images. First, the proposed methodology leverages the power of deep generative models (DGMs) to learn the statistical distribution of the endmembers based on the spectral signatures available in the existing libraries. Afterwards, new samples can be drawn from the learned EM distributions and used to augment the spectral libraries, improving the overall quality of the unmixing process. Experimental results using synthetic and real data attest the superior performance of the proposed method even under library mismatch conditions.