Polychlorinated naphthalenes (PCNs) are legacy contaminants that are listed by the Stockholm convention, initially for reduction of inadvertent production and ultimately, for elimination. They originate through releases from older electrical equipment, inadvertent contamination in industrial chemicals and from combustion processes such as incineration. Recent advances in measurement techniques have allowed a greater characterisation of PCN occurrence, yielding more specific data including individual PCN congener concentrations. Emerging data on food shows widespread occurrence in most commonly consumed foods from different parts of the world. Concurrently, toxicological studies have also allowed a greater insight into the potencies of some congeners, a number of which are known to elicit potent, aryl hydrocarbon receptor (AhR) mediated responses, often referred to as dioxin-like toxicity. The dietary pathway is widely recognised as the most likely route to non-occupational human exposure. This paper reviews some of the more recent findings on PCN occurrence in food, biota, and human tissues, and discusses the use of relative potencies to express PCN toxicity in foods.