Plant growth is often limited by highly activated aluminum (Al) and low available phosphorus (P) in acidic soil. Ectomycorrhizal (ECM) fungi can improve their host plants' Al tolerance by increasing P availability while decreasing Al activity in vitro or in hydroponic or sand culture systems. However, the effect of ECM fungi on inorganic P (IP) and labile Al in acidic soil in the field, particularly in conjunction with Al treatment, remains poorly understood. The present study aimed to determine the influence of ECM fungal association on the mobilization of IP and labile Al in rhizosphere soil of host plants grown in the field with external Al treatment and the underlying nutritional mechanism in plant Al tolerance. To do so, 4-week-old Pinus massoniana seedlings were inoculated with three ECM isolates (Laccaria bicolor 270, L. bicolor S238A, and L. bicolor S238N) and grown in a Haplic Alisol field with or without Al treatment for 12 weeks. Results showed that L. bicolor association enhanced the available P depletion and facilitated the mobilization of IP and labile Al, in turn improving the capacity of host plant to use Al-bound P, Ca-bound P, and occluded P, particularly when P. massoniana seedlings were inoculated with L. bicolor S238A. Inoculation with L. bicolor isolates also enhanced the solubility of labile Al and facilitated the conversion of acid-soluble Al into exchangeable Al. Our findings suggested that ECM inoculation could enhance plant Al tolerance in the field by mobilizing IP to improve the P bioavailability but not by decreasing Al activity.IMPORTANCE Here, we reveal the underlying nutritional mechanism in plant Al tolerance conferred by ectomycorrhizal (ECM)-fungus inoculation in the field and report the screening of a promising ECM isolate to assist phytoremediation and afforestation using Pinus massoniana in acidic soil in southern China. This study advances our understanding of the contribution of ECM fungi to plant-ECM-fungus symbiosis and highlights the vital role of ECM-fungus inoculation in plant Al tolerance. In addition, the results described in the present study confirm the importance of carrying out studies in the field rather than only in vitro studies. Our findings strengthen our understanding of the role of ECM-fungus association in detecting, utilizing, and transporting unavailable nutrients in the soil to enhance host plant growth and adaptability in response to adverse habitats.