A 9‐week greenhouse pot experiment was carried out to study polychlorinated biphenyl (PCB) dissipation and mung bean (Vigna radiata (L.) Wilczek) growth in a PCB‐contaminated soil. Besides the control (i.e., monoculture of mung bean), four treatments were tested: intercropping with ryegrass (Lolium perenne L.) (IL) and IL treated with arbuscular mycorrhizal (AM) fungus Funneliformis caledonium (+M), nanoscale zero‐valent iron (nZVI) (+N), and both (+NM). Compared with the control, the interspecific competition on soil nutrients besides growth space upon IL tended to decrease the seed yield of mung bean, since the P acquisition by ryegrass, the dominant species, was about 17 times that by mung bean. On the one hand, +N significantly enhanced the dissipation of homologs with three or more chlorine atoms and total PCBs in the soil, consuming a quantity of H+ and increasing soil pH. On the other hand, +N negatively influenced soil available P concentration, mycorrhizal colonization, mung bean seed yield, and ryegrass shoot biomass. In contrast, +M significantly increased mycorrhizal colonization of both plants and ALP activity of the soil, tended to improve plant total P acquisition, and even powerfully enhanced the dissipation of highly chlorinated homologs. In the case of +N, +M again significantly accelerated mycorrhization of both plants and tended to elevate ALP activity of the soil, but the adsorption of soil available P by nZVI debilitated the P benefit from AM fungi. However, +M still tended to improve not only ryegrass shoot biomass but also mung bean seed yield, suggesting that AM fungus had induced detoxification of both host plants against nZVI. In addition, the phytoremediation efficiency of ryegrass associated with AM fungi, which was greatly inhibited by the amendment of nZVI, was reactivated by the newly inoculated AM fungus. These results indicated that when intercropping of edible crops with remedial plants, nZVI and AM fungus played absolutely differential roles during the remediation of PCB‐contaminated soils.