Dual-energy computed tomography (DECT) is an advanced form of computed tomography (CT), in which image acquisition is performed at two different energy spectra, instead of a single-energy spectrum using conventional single-energy CT (SECT). This enables the creation of different reconstructions and quantitative spectral tissue analysis beyond what is possible with SECT. In adults, there are increasing clinical applications of DECT for all organ systems, including neuroimaging and head and neck imaging. However, there are relatively few studies evaluating applications of DECT for pediatric imaging and little to none in neuroimaging or head and neck imaging. The purpose of this article is to provide an overview and familiarize the readers with DECT. This article will review the fundamental principles behind DECT, including different DECT acquisition systems and principles of DECT material characterization. This will be followed by a review of potential applications of DECT, many based on imaging the head and neck. The objectives are to familiarize the readers with this exciting technology and hopefully serve as a primer for investigations and applications of DECT for pediatric neuro and head and neck imaging.