This review updates information on the historical manufacture and unintentional production of polychlorinated naphthalenes (PCNs). The direct toxicity of PCNs as a result of occupational human exposure and through contaminated feed in livestock was recognised decades ago, making PCNs a precursor chemical for consideration in occupational medicine and occupational safety. This was confirmed by the listing of PCNs by the Stockholm Convention as a persistent organic pollutant in the environment, food, animals and humans. PCNs were manufactured globally between 1910 ~ 1980, but reliable data on the volumes produced or national outputs are scarce. A total figure for global production would be useful for the purposes of inventory and control and it is clear that combustion related sources such as waste incineration, industrial metallurgy and use of chlorine are current major sources of PCNs to the environment. The upper bound estimate of total global production has been put at 400,000 metric tons but the amounts (at least, many 10s of tonnes) that are currently emitted unintentionally every year through industrial combustion processes should also be inventoried along with estimates for emissions from bush and forest fires. This would however require considerable national effort, financing and co-operation from source operators. The historical (1910–1970s) production and resulting emissions through diffusive/evaporative releases through usage, are still reflected in documented occurrence and patterns of PCNs in human milk in Europe and other locations worldwide. More recently, PCN occurrence in human milk from Chinese provinces has been linked to local unintentional emissions from thermal processes.