A passive air sampling network has been established to investigate polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at Global Atmospheric Passive Sampling (GAPS) sites and six additional sites in the Group of Latin American and Caribbean Countries (GRULAC) region. The air sampling network covers background, agricultural, rural, and urban sites. Samples have been collected over four consecutive periods of 6 months, which started in January 2011 [period 1 (January to June 2011), period 2 (July to December 2011), period 3 (January to June 2012), and period 4 (July 2012 to January 2013)]. Results show that (i) the GAPS passive samplers (PUF disk type) and analytical methodology are adequate for measuring PCDD/F burdens in air and (ii) PCDD/F concentrations in air across the GRULAC region are widely variable by almost 2 orders of magnitude. The highest concentrations in air of Σ4-8PCDD/Fs were found at the urban site São Luis (Brazil, UR) (i.e., 2560 fg/m3) followed by the sites in São Paulo (Brazil, UR), Mendoza (Argentina, RU), and Sonora (Mexico, AG) with values of 1690, 1660, and 1610 fg/m3, respectively. Very low concentrations of PCDD/Fs in air were observed at the background site Tapanti (Costa Rica, BA), 10.8 fg/m3. This variability is attributed to differences in site characteristics and potential local/regional sources as well as meteorological influences. The measurements of PCDD/Fs in air agree well with model-predicted concentrations performed using the Global EMEP Multimedia Modeling System (GLEMOS) and emission scenario constructed on the basis of the UNEP Stockholm Convention inventory of dioxin and furan emissions.