Preprocessing is a major area of interest in the field of hyperspectral endmember extraction, for it can provide a few high-quality candidates for fast endmember extraction without sacrificing endmember accuracy. We propose a superpixel-guided preprocessing (SGPP) algorithm to accelerate endmember extraction based on spatial compactness and spectral purity analysis. The proposed SGPP first transforms a hyperspectral image into low-dimension data using principal component analysis. SGPP then utilizes the superpixel method, which normally has linear complexity, to segment the first three components into a set of superpixels. Next, SGPP transforms low-dimension superpixels into noise-reduced superpixels and calculates their spatial compactness and spectral purity based on Tukey’s test and data convexity. SGPP finally retains a few high-quality pixels from each superpixel with high spatial compactness and spectral purity indices for subsequent endmember identification. Based on the spectral angle distance, root-mean-square error, and speedup, experiments are conducted on synthetic and real hyperspectral datasets, and they indicate that SGPP is superior to current state-of-the-art preprocessing techniques.