Electron spin resonance (ESR), or electron paramagnetic resonance (EPR), is an analytical technique that can extract a great deal of information from any material containing unpaired electrons. This article explains how ESR works and where it applies in materials characterization. It describes a typical ESR spectrometer and explains how to tune it to optimize critical electromagnetic interactions in the test sample. It also identifies compounds and elements most suited for ESR analysis and explains how to extract supplementary information from test samples based on the time it takes electrons to return to equilibrium from their resonant state. Two of the most common methods for measuring this relaxation time are presented as are several application examples.