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Spectral mixture analysis is probably the most commonly used approach among sub-pixel analysis techniques. This method models pixel spectra as a linear combination of spectral signatures from two or more ground components. However, spectral mixture analysis does not account for the absence of one of the surface features or spectral variation within pure materials since it utilizes an invariable set of surface features. Multiple endmember spectral mixture analysis (MESMA), which addresses these issues by allowing endmembers to vary on a per pixel basis, was employed in this study to model Landsat ETM+ reflectance in the Phoenix metropolitan area. Image endmember spectra of vegetation, soils, and impervious surfaces were collected with the use of a fine resolution Quickbird image and the pixel purity index. This study employed 204 (3 x 17 x 4) total four-endmember models for the urban subset and 96 (6 x 6 x 2 x 4) total five-endmember models for the non-urban subset to identify fractions of soil, impervious surface, vegetation and shade. The Pearson correlation between the fraction outputs from MESMA and reference data from Quickbird 60 cm resolution data for soil, impervious, and vegetation were 0.8030, 0.8632, and 0.8496 respectively. Results from this study suggest that the MESMA approach is effective in mapping urban land covers in desert cities at sub-pixel level.