The primitive electronic waste (e-waste) recycling has brought a series of environmental pollutants in Guiyu, China. Antimony is one of the important metal contaminants and has aroused the global concerns recently. We aimed to investigate concentrations of antimony in human hair from Guiyu and compared them with those from a control area where no e-waste recycling exists, and assessed the potential risk factors. A total of 205 human hair samples from Guiyu and 80 samples from Jinping were collected for analysis. All volunteers were asked to complete a questionnaire including socio-demographic characteristics and other possible factors related to hair antimony exposure. The concentrations of hair antimony were analyzed using atomic absorption spectrophotometer. Our results indicated that the level of hair antimony in volunteers from Guiyu (median, 160.78; range, 6.99-4412.59 ng/g) was significantly higher than those from Jinping (median, 61.74; range, 2.98-628.43 ng/g). The residents who engaged in e-waste recycling activities in Guiyu had higher hair antimony concentrations than others (P < 0.001). There was no significant difference of hair antimony concentrations among different occupation types in e-waste recycling. Multiple stepwise regression analysis indicated that hair antimony concentrations were associated with education level (β = -0.064), the time of residence in Guiyu (β = 0.112), living house also served as e-waste workshop (β = 0.099), the work related to e-waste (β = 0.169), and smoking (β = 0.018). The elevated hair antimony concentrations implied that the residents in Guiyu might be at high risk of antimony contamination, especially the e-waste recycling workers. Work related to e-waste recycling activities and long-time residence in Guiyu contributed to the high hair antimony exposure.