Arbuscular mycorrhizal fungi (AMF)-assisted phytoremediation is a promising technology for sustainable removal of hazardous pollutants like dioxins/furans (PCDD/F) from the soil. However, little is known on AMF development in the presence of the persistent organic pollutants, PCDD/F. Thus, the present work aims at investigating the impact of increasing PCDD/F concentrations on the development of both partners of the symbiosis: the AMF, Rhizophagus irregularis and the chicory roots, Cichorium intybus L. grown under axenic conditions. Our results show that even R. irregularis spore germination is not affected by PCDD/F, it occurred mainly in linear way. However, root colonization, extra-radical hyphal elongation and sporulation are reduced by 40, 30, and 75%, respectively, at the highest PCDD/F concentration. In addition, while non-mycorrhizal root growth (length and dry weight) decreased at the highest PCDD/F concentration, no negative effect was observed on the dry weight of mycorrhizal roots. In conclusion, our findings show that although high PCDD/F concentrations disturb the main stages of R. irregularis development, the AMF remains able to fulfill its life cycle in the presence of PCDD/F. Moreover, the mycorrhizal inoculation protects the host plant against PCDD/F phytotoxicity. AMF could thus represent an interesting amendment option to assist phytoremediation of PCDD/F contaminated soils.