Aqueous arsenic speciation, or the chemical forms in which arsenic exists in water, is a challenging, interesting, and complicated aspect of environmental arsenic geochemistry. Arsenic has the ability to form a wide range of chemical bonds with carbon, oxygen, hydrogen, and sulfur, resulting in a large variety of compounds that exhibit a host of chemical and biochemical properties. Besides the intriguing chemical diversity, arsenic also has the rare capacity to capture our imaginations in a way that few elements can duplicate: it invokes images of foul play that range from sinister to comedic (e.g., “inheritance powder” and arsenic-spiked elderberry wine). However, the emergence of serious large-scale human health problems from chronic arsenic exposure in drinking water has placed a high priority on understanding environmental arsenic mobility, toxicity, and bioavailability, and chemical speciation is key to these important questions. Ultimately, the purpose of arsenic speciation research is to predict future occurrences, mitigate contamination, and provide successful management of water resources.