Organophosphate esters (OPEs) are normally used as flame retardants, plasticizers and lubricants, but have become environmental pollutants. Because OPEs are normally present alongside heavy metals in soils, the effects of interactions between OPEs and heavy metals on plant uptake of OPEs need to be determined. In this study, we investigated the effects of OPEs chemical structure, plant cultivar and copper (Cu) on the uptake and translocation of OPEs by plants. The bioaccumulation of OPEs varied among plant cultivars. They were preferentially enriched in carrot, with the lowest concentrations observed in maize. OPEs with electron-ring substituents (ER-OPEs) exhibited a higher potential for root uptake than did OPEs with open-chain substituents (OC-OPEs), which could be attributed to the higher sorption of ER-OPEs onto root charged surfaces. This was explained by the stronger noncovalent interactions with the electron-rich structure of ER-OPEs. The presence of Cu slightly reduced the distinct difference in the ability of roots to take up OC-OPEs and ER-OPEs. This was explained by the interactions of Cu ions with the electron-rich structure of ER-OPEs, which suppressed the sorption of ER-OPEs on the root surface. A negative relationship between the logarithms of the translocation factor and octanol-water partition coefficient (Kow) was observed in treatments with either OPEs only or OPEs + Cu, implying the significant role of hydrophobicity in the OPEs acropetal translocation. The results will improve our understanding of the uptake and translocation of OPEs by plant cultivars as well as how the process is affected by the chemical structure of OPEs and Cu, leading to improvements in the ecological risk assessment of OPEs in the food chain.