Phytoremediation-assisted electrokinetic-bioremediation is a novel technology for soil remediation. We aimed to study the effects of a plant (ryegrass) on electrokinetic-bioremediation in n-hexadecane-contaminated soil. After treatment for 40 days, the n-hexadecane degradation ratio of electrokinetic-bioremediation-ryegrass (EK-Bio-RG) was 4.86% higher than that of electrokinetic-bioremediation (EK-Bio) (p < 0.05), with a maximum constant degradation rate (107.23 ± 4.62 mg kg· d). Owing to the improved electrical conductivity, 73.28% of the initial current was maintained on the 40th day in EK-Bio-RG, which was 1.62 times that in EK-Bio. Furthermore, ryegrass reduced the soil zeta potential, which indicated the alleviation of the soil electric double layer compression and prevention of the aggregation of small soil colloids into larger ones. The fine colloidal structure was conducive to mass transfer in electrokinetic-bioremediation. An analysis of the microbial community showed that the degradation of n-hexadecane was mainly attributable to gram-positive bacteria, and a new microbial community was gradually constructed in the rhizosphere, which still metabolized n-hexadecane. The results indicated that the sustainability of the electrokinetic effect was improved combined with ryegrass, and the harmonious micro-environment in the rhizosphere was constructed which furtherly optimized the EK-Bio technology to remediate organics-polluted soil.