Although polychlorinated biphenyls are no longer sold as commercial mixtures, they are still being produced through modern manufacturing processes. We have previously shown that non-Aroclor PCB11 is prevalent in indoor and outdoor air, sediment, and detected in human serum. Here we report the prevalence of non-Aroclor PCB congeners (≤0.20 weight percent in Aroclor) in human serum collected from urban and rural adolescents and their mothers. We hypothesized that additional non-Aroclors congeners are present in serum. Sera were extracted and detected for 209 PCBs using gas chromatography-tandem mass spectrometry. A list of 70 non-Aroclor PCB congeners was determined by measurement of original Aroclors. PCB 11, 14, 35 and 209 are the major dominating and most frequently detected congeners. PCB 14 and 35 have not been previously reported for environmental matrices. Adolescents have significantly lower total non-Aroclor PCBs concentration than mothers in East Chicago (p<0.001) and Columbus Junction (p=0.008). There are significant differences in non-Aroclor PCBs between East Chicago community and Columbus Junction community (p<0.001). Non-Aroclor PCBs represent an average of 10% (and up to 50%) of total PCBs measured in serum. An average of 50% (and up to 100%) of these concentrations may attribute to aryl azo and phthalocyanine paint pigments.