The composition of clay minerals in soils, and more particularly the presence of montmorillonite (as part of the smectite family), is a key factor in soil swell-shrinking as well as off-road vehicle mobility. Detecting these topsoil clay minerals and quantifying the montmorillonite abundance are a challenge since they are usually intimately mixed with other minerals, soil organic carbon and soil moisture content. Imaging spectroscopy coupled with unmixing methods can address these issues, but the quality of the estimation degrades the coarser the spatial resolution is due to pixel heterogeneity. With the advent of UAV-borne and proximal hyperspectral acquisitions, it is now possible to acquire images at a centimeter scale. Thus, the objective of this paper is to evaluate the accuracy and limitations of unmixing methods to retrieve montmorillonite abundance from very-high-resolution hyperspectral images (1.5 cm) acquired from a camera installed on top of a bucket truck over three different agricultural fields, in Loiret department, France. Two automatic endmember detection methods based on the assumption that materials are linearly mixed, namely the Simplex Identification via Split Augmented Lagrangian (SISAL) and the Minimum Volume Constrained Non-negative Matrix Factorization (MVC-NMF), were tested prior to unmixing. Then, two linear unmixing methods, the fully constrained least square method (FCLS) and the multiple endmember spectral mixture analysis (MESMA), and two nonlinear unmixing ones, the generalized bilinear method (GBM) and the multi-linear model (MLM), were performed on the images. In addition, several spectral preprocessings coupled with these unmixing methods were applied in order to improve the performances. Results showed that our selected automatic endmember detection methods were not suitable in this context. However, unmixing methods with endmembers taken from available spectral libraries performed successfully. The nonlinear method, MLM, without prior spectral preprocessing or with the application of the first Savitzky-Golay derivative, gave the best accuracies for montmorillonite abundance estimation using the USGS library (RMSE between 2.2-13.3% and 1.4-19.7%). Furthermore, a significant impact on the abundance estimations at this scale was in majority due to (i) the high variability of the soil composition, (ii) the soil roughness inducing large variations of the illumination conditions and multiple surface scatterings and (iii) multiple volume scatterings coming from the intimate mixture. Finally, these results offer a new opportunity for mapping expansive soils from imaging spectroscopy at very high spatial resolution.