Nitroxyl (HNO), the 1-electron reduced and protonated congener of nitric oxide (NO), has received recent attention as a potential pharmacological agent for the treatment of heart failure and as a preconditioning agent for the mitigation of ischemia-reperfusion injury. Interest in the pharmacology and biology of HNO has prompted examination, or in some instances reexamination, of many of its chemical properties. Such studies have provided insight into the chemical basis for the biological effects of HNO, although the biochemical mechanisms for many of these effects remain to be established. In this review, a brief description of the biologically relevant chemistry of HNO is given, followed by a more detailed discussion of the pharmacology and potential toxicology of HNO.