Coal fly ash (CFA) is an industrial waste generated in huge amounts worldwide, and the management of CFA has become an environmental concern. Recovery of valuable metals from CFA is one of the beneficial reuse options of CFA. Rhenium (Re) is one of the rarest metals in the Earth's crust and one of the most expensive metals of strategic significance in the world market. A CFA at the Jungar Thermal Power Plant, Inner Mongolia, China, contains more Re than two alkaline soils in the surrounding region. Pot experiments were undertaken to grow lucerne (Medicago sativa) and erect milkvetch (Astragalus adsurgens) in a loessial soil and an aeolian sandy soil amended with different rates (5%, 10%, 20%, and 40%) of CFA. The results show that plant growth was considerably enhanced and Re concentration in plants was significantly increased when CFA was applied to the alkaline soils at rates of ≤20%; while in some cases plant growth was also markedly enhanced by the 40% CFA treatment, which increased plant Re concentration the most of all treatments. Both lucerne and erect milkvetch showed potential for phytoextracting Re from CFA-amended alkaline soils. Using CFA for soil amendment not only offers a potential solution for the waste disposal problem of CFA, but the phytoextraction of Re by both lucerne and erect milkvetch may also bring an economic profit in the future.