Air concentrations of polychlorinated naphthalenes (PCNs) were measured as part of the Global Atmospheric Passive Sampling (GAPS) study to assess their spatial distribution on a worldwide basis for the first sampling period between December 2004 and March 2005. Results from more than 40 sites on seven continents show that PCNs are widespread, and highest levels are detected in urban/industrial locations consistent with other air sampling studies. The geometric mean air concentration of ΣPCN is 1.6 pg/m3, ranging from below detection limit to 32 pg/m3. With technical PCN mixtures largely no longer produced, combustion inputs may be contributing increasingly to contemporary PCN air burden globally. Enrichment of combustion-related congeners, e.g., PCN-52/60, -50, -51, -54, and -66/67, is observed in the congeneric compositions of air at nearly all sites compared to relatively minor contribution of these congeners in technical PCN formulations. Further evidence of current combustion sources influencing global PCN levels is a higher relative abundance of combustion-related congeners quantified by ΣPCNcombustion/ΣPCN. The relative contribution by combustion sources and emissions from technical PCN mixtures is expected to vary among sites since it depends on the combustion sources and the technical mixture used in a particular country or region.