PCDD/Fs (17 congeners and Σ tetra -to octachloro homologues) and 209 PCBs were investigated in monthly samples of ambient air (gas + particle phase) and atmospheric deposition at two background monitoring sites in Germany in 2018/19. In atmospheric deposition samples, PCDD/F congeners as well as certain PCBs were frequently below the method quantification limits whereas values for PCDD/F homologue groups could be quantified more often. Annual deposition averages for individual PCDD/Fs were between <0.1 μg/m2d and 6.7 μg/m2d. Averages for Σ TeCDD/F to OCDD/F homologue totals in deposition were about 11 pg/m2d and 19 pg/m2d. Total PCB deposition rates were about 1900 pg/m2d and 1550 pg/m2d. PCDD/F + PCB-deposition rates were below 1 pg WHO2005-TEQ/m2d on average. In ambient air, both substance groups were frequently observed. Annual concentration averages for individual PCDD/F were between 0.1 fg/m³ and 50 fg/m³. Average values for Σ TeCDD/F to OCDD/F homologue totals in ambient air were 283 fg/m³ and 162 fg/m³. Total PCB concentrations were about 50 pg/m³ at both sites. PCDD/F + PCB-TEQ values were lower than 5 fg WHO2005-TEQ/m³ on average. Besides the frequently studied dioxin-like PCBs and six indicator PCBs, the analysis of the 209 PCBs (166 separated PCB-peaks) enabled the identification and evaluation of additional PCBs that might be of environmental concern. Of 166 PCBs or PCB-coelutions, up to 144 were quantified in air samples and up to 94 in atmospheric deposition samples. In ambient air, some of these PCBs were observed at levels similar to or exceeding those of the six indicator PCBs. Important additional PCBs in ambient air were PCB 5 + 8, PCB 11, PCB 17, PCB 18, PCB 20 + 33, PCB 31, PCB 43 + 49, PCB 44, PCB 47 + 48 + 65 + 75, PCB 93 + 95 + 98 + 102, PCB 139 + 149, and PCB 151. The presence of these PCBs in atmospheric samples implies that by analysing only selected PCBs potentially important contaminants are overlooked.