This paper investigates the hybrid technology of electrokinetics (EK) coupled with bioremediation (Bio) in the removal of pyrene (PYR) in a soil matrix. Five different treatments were conducted to investigate the coupling interactions between EK and Bio on PYR degradation. A simulated removal curve was obtained by combining the degradation curves in EK- and Bio-only experiments. The results show that the simulated curve fitted well with the actual degradation curve in electro-bioremediation (EK-Bio) experiments for the first 30 days of the experiment, while at later stages a discrepancy was found. This discrepancy was caused by adverse effects of low soil pH (3.6) near the anode on bacteria health during EK treatments. With polarity reversal (PR) to control the soil pH, the simulated curve fitted very well (r > 0.99) with the actual degradation curve during the whole treatment period. At the end of the experiment, PYR removal amounted to 63% with EK-Bio treatments in PR electric fields, which was 1.7 times that of Bio-only. Moreover, the bacteria counts under electric fields were more than that without EK. The spatial distributions of PYR degradation and bacterial counts were also investigated. The results show that they were both higher nearer the electrodes under PR electric fields.