Imaging spectroscopy is a tool that can be used to spectrally identify and spatially map materials based on their specific chemical bonds. Spectroscopic analysis requires significantly more sophistication than has been employed in conventional broadband remote sensing analysis. We describe a new system that is effective at material identification and mapping: a set of algorithms within an expert system decision‐making framework that we call Tetracorder. The expertise in the system has been derived from scientific knowledge of spectral identification. The expert system rules are implemented in a decision tree where multiple algorithms are applied to spectral analysis, additional expert rules and algorithms can be applied based on initial results, and more decisions are made until spectral analysis is complete. Because certain spectral features are indicative of specific chemical bonds in materials, the system can accurately identify and map those materials. In this paper we describe the framework of the decision making process used for spectral identification, describe specific spectral feature analysis algorithms, and give examples of what analyses and types of maps are possible with imaging spectroscopy data. We also present the expert system rules that describe which diagnostic spectral features are used in the decision making process for a set of spectra of minerals and other common materials. We demonstrate the applications of Tetracorder to identify and map surface minerals, to detect sources of acid rock drainage, and to map vegetation species, ice, melting snow, water, and water pollution, all with one set of expert system rules. Mineral mapping can aid in geologic mapping and fault detection and can provide a better understanding of weathering, mineralization, hydrothermal alteration, and other geologic processes. Environmental site assessment, such as mapping source areas of acid mine drainage, has resulted in the acceleration of site cleanup, saving millions of dollars and years in cleanup time. Imaging spectroscopy data and Tetracorder analysis can be used to study both terrestrial and planetary science problems. Imaging spectroscopy can be used to probe planetary systems, including their atmospheres, oceans, and land surfaces.