Surface soils from Guiyu, China (an intense e-waste processing center) were analyzed for persistent organic pollutants (POPs) and variations in composition of the resident bacterial communities. Denaturing Gradient Gel Electrophoresis analysis of bacterial 16S rRNA gene showed that e-waste pollution altered the bacterial community structure by promoting changes in species composition and species richness. Bacterial diversity was not decreased at e-waste open-burning sites, compared with a non e-waste site (reservoir site), due to flourishing of possible POPs-consuming bacterial cohorts. PAH-incubated experiments confirmed that different levels of PAHs might affect the bacterial community by suppressing or favoring certain groups of bacteria, for instance, uncultured Clostridium sp. and Massilia sp., respectively. Taxonomic analysis indicated beta-proteobacteria and Firmicutes were abundant bacterial lineages in PAH-polluted soils. This study is the first reporting bacterial community structures at e-waste processing sites, and indicated that crude processing of e-waste has become a biohazard to the terrestrial environment warranting more extensive studies of microbial communities at e-waste polluted environments.