The effort to map terrestrial biodiversity, in recent years limited mostly to the use of broadband multispectral remote sensing at decameter scales, can be greatly enhanced by harnessing hyperspectral imagery. Interpretation of hyperspectral imagery may be aided by the Mixture Residual (MR) spectral preprocessing transformation. MR integrates the benefits of spectral mixture analysis with the absorption peak-enhancing characteristics of continuum removal. MR characterizes each pixel as a linear combination of generic end-members estimating the spectral continuum, from which the residual of each wavelength is computed and treated as a source of additional information. Using Hyperspectral Precursor of the Application Mission (PRISMA) imagery, we tested the ability of MR-transformed reflectance as compared to untransformed surface reflectance (SR) to map plant associations and land cover using ground truthing and random forest classifications across four landscapes within the North American Coastal Plain. We used a forward stepwise selection algorithm to choose bands for each classification and subsequently compared these between SR and MR. Our MR classifications distinguished land cover with 5% greater balanced accuracy on average than the SR-based classifications across all four landscapes. The MR-based classification that integrated data from all landscapes into a unified model encompassing all 21 land cover types achieved a 76% average balanced accuracy over three iterations. Generally, MR utilized the near-infrared region to a greater degree than SR while deemphasizing the green peak. Based on our results, MR improves the accuracy of mapping terrestrial biodiversity, likely extending to other current and planned satellite hyperspectral missions.