Display omitted •Endmember extraction and soft modeling in hyperspectral Raman imaging are compared.•Three simulated cases, a pharmaceutical sample, and plastic foils were studied.•VCA outputs can be used as initialization for MCR-ALS.•Pure pixels are required for extracting pure variables by VCA, but not for MCR-ALS. Hyperspectral Raman imaging not only offers spectroscopic fingerprints but also reveals morphological information such as spatial distributions in an analytical sample. However, the spectrum-per-pixel nature of hyperspectral imaging (HSI) results in a vast amount of data. Furthermore, HSI often requires pre- and post-processing steps to extract valuable chemical information. To derive pure spectral signatures and concentration abundance maps of the active spectroscopic compounds, both endmember extraction (EX) and Multivariate Curve Resolution (MCR) techniques are widely employed. The objective of this study is to carry out a systematic investigation based on Raman mapping datasets to highlight the similarities and differences between these two approaches in retrieving pure variables, and ultimately provide guidelines for pure variable extraction. Numerical simulations and Raman mapping experiments on a mixture of pharmaceutical powders and on a layered plastic foil sample were conducted to underscore the distinctions between MCR and EX algorithms (in particular Vertex Component Analysis, VCA) and their outputs. Both methods were found to perform well if the dataset contains pure pixels for each of the individual components. However, in cases where such pure pixels do not exist, only MCR was found to be capable of extracting the pure component spectra.