In this article, polyaniline (PANI) nanofibers were prepared and added to low-density polyethylene (LDPE) to produce PANI nanofibers/LDPE composites. LDPE and the composites were tested for direct current (DC) conductivity, breakdown strength, and space charge characteristics. The results suggested that DC breakdown strength of PANI nanofibers/LDPE composites significantly declined once PANI was added, and the decline was more evident with the increase of PANI nanofibers. Meanwhile, the addition of PANI nanofibers contributed to a decrease in the conductivity of LDPE. As the content of PANI nanofibers increased, the conductivity of the composites declined first and then raised. DC conductivity properties of LDPE could be improved by adding an appropriate amount of PANI nanofibers. Compared with LDPE, the space charge distribution was changed in LDPE due to the addition of PANI nanofibers. With the increase of content of PANI nanofibers, the amount of space charges close to the electrodes decreased gradually.