Climate change and anthropogenic pressure are causing an indisputable decline in biodiversity; therefore, the need of environmental knowledge is important to develop the appropriate management plans. In this context, remote sensing and, specifically, hyperspectral imagery (HSI) can contribute to the generation of vegetation maps for ecosystem monitoring. To properly obtain such information and to address the mixed pixels inconvenience, the richness of the hyperspectral data allows the application of unmixing techniques. In this sense, a problem found by the traditional linear mixing model (LMM), a fully constrained least squared unmixing (FCLSU), is the lack of ability to account for spectral variability. This paper focuses on assessing the performance of different spectral unmixing models depending on the quality and quantity of endmembers. A complex mountainous ecosystem with high spectral changes was selected. Specifically, FCLSU and 3 approaches, which consider the spectral variability, were studied: scaled constrained least squares unmixing (SCLSU), Extended LMM (ELMM) and Robust ELMM (RELMM). The analysis includes two study cases: 1) robust endmembers and 2) nonrobust endmembers. Performances were computed using the reconstructed root-mean-square error (RMSE) and classification maps taking the abundances maps as inputs. It was demonstrated that advanced unmixing techniques are needed to address the spectral variability to get accurate abundances estimations. RELMM obtained excellent RMSE values and accurate classification maps with very little knowledge of the scene and minimum effort in the selection of endmembers, avoiding the curse of dimensionality problem found in HSI.