Phytoremediation, use of plants for remediation, is an emerging technology for treating heavy metals or a final polishing step for the high-level organic contamination, and may be suitable for remediation of heavy metal and organic co-contaminated soil. The aim of this study was to investigate the influence of co-contamination on the growth of Zea mays L. and the fate of both heavy metal and organic pollutants, using Cu and pyrene as the model pollutants. Results showed that shoot and root biomass were affected by the copper-pyrene co-contamination, although maize grown in spiked soils showed no outward signs of phytotoxicity. With the initial concentration of 50,100 and 500 mg/kg, pyrene tended to alleviate the inhibition of Cu to Z. mays L. Pyrene in both planted and non-planted soil was greatly decreased at the end of the 4-week culture, accounting for 16-18% of initial extractable concentrations in non-planted soil and 9-14% in planted soil, which indicated that the dissipation of soil pyrene was enhanced in the presence of vegetation probably due to the biodegradation and association with the soil matrix. With the increment of Cu level, residual pyrene in the planted soil tended to increase. The pyrene residual in the presence of high concentration of Cu was even higher in the planted soil than that in the non-planted soil, which suggested that the change of the microbial composition and microbial activity or the modified root physiology under Cu stress was probably unbeneficial to the dissipation of pyrene. A more thorough understanding of the mechanisms by which metals affect the dissipation of organic pollutants in the rhizosphere could provide a much better framework on which to base manipulation. Unlike pyrene, heavy metal copper cannot be degraded. Decontamination of Cu from contaminated soils in this system required the removal of Cu by plants. It was observed that the ability of Cu phytoextraction would be inhibited under co-contamination of high level of pyrene in highly Cu-polluted soil. In the treatment of 400 mg Cu/kg and 500 mg pyrene/kg, the accumulation of Cu was less than half of that in 400 mg Cu/kg treatment.