In this paper, we present a method for hyperspectral retrieval using multispectral satellite images. The method consists of the use of training spectral data with a compressive capability. By using principal component analysis (PCA), a proper number of basis vectors are extracted. These vectors are properly combined and weighted by the sensors’ responses from visible MODIS channels, achieving as a result the retrieval of hyperspectral images. Once MODIS channels are used for hyperspectral retrieval, the training spectra are projected over the recovered data, and the ground-based process used for training can be reliably detected. To probe the method, we use only four visible images from MODIS for large-scale ash clouds’ monitoring from volcanic eruptions. A high-spectral resolution data of reflectances from ash was measured in the laboratory. Using PCA, we select four basis vectors, which combined with MODIS sensors responses, allows estimating hyperspectral images. By comparing both the estimated hyperspectral images and the training spectra, it is feasible to identify the presence of ash clouds at a pixel-by-pixel level, even in the presence of water clouds. Finally, by using a radiometric model applied over hyperspectral retrieved data, the relative concentration of the volcanic ash in the cloud is obtained. The performance of the proposed method is compared with the classical method based on temperature differences (using infrared MODIS channels), and the results show an excellent match, outperforming the infrared-based approach. This proposal opens new avenues to increase the potential of multispectral remote systems, which can be even extended to other applications and spectral bands for remote sensing. The results show that the method could play an essential role by providing more accurate information of volcanic ash spatial dispersion, enabling one to prevent several hazards related to volcanic ash where volcanoes’ monitoring is not feasible.