Comparisons of polyvinyl chloride electrical tape typically rely upon evaluating class characteristics such as physical dimensions, surface texture, and chemical composition. Given the various techniques that are available for this purpose, a comprehensive study has been undertaken to establish an optimal analytical scheme for electrical tape comparisons. Of equal importance is the development of a quantitative means for sample discrimination. In this study, 67 rolls of black electrical tape representing 34 different nominal brands were analyzed via scanning electron microscopy and energy dispersive spectroscopy. Differences in surface roughness, calendering marks, and filler particle size were readily apparent, including between some rolls of the same nominal brand. The relative amounts of magnesium, aluminum, silicon, sulfur, lead, chlorine, antimony, calcium, titanium, and zinc varied greatly between brands and, in some cases, could be linked to the year of manufacture. For the first time, quantitative differentiation of electrical tapes was achieved through multivariate statistical techniques, with 36 classes identified within the sample population. A single-blind study was also completed where questioned tape samples were correctly associated with known exemplars. Finally, two case studies are presented where tape recovered from an improvised explosive device is compared with tape recovered from a suspect.