Two smelters in the North of France emitted potentially toxic metals for more than a century and today, the resulting contamination represents a risk to human health and affects also the biodiversity. To limit health risks and to improve the soil quality, a study using calcium phosphates (monocalcium phosphate, dicalcium phosphate and a mixture of both salts) and Lolium perenne L was conducted. Through this preliminary investigation, we will try to shed some light about (i) the effects of a sustainable amount of calcium phosphates on the agronomic, biological (microbial and fungi communities) and physiological parameters (chlorophyll a and b, antocyanins, carotenoids) as well as the phytoavailability of potentially toxic metals and nutrients in time, and (ii) the potential use of contaminated biomass from ryegrass as a source of new valorisation ways instead of using it as contaminated compost by gardeners. Although slight variations in pH and significant increases of assimilable phosphorus after adding calcium phosphates were registered, the physiology of plants and the biological parameters were statistically unchanged. The germination of the ryegrass seeds was favoured with calcium phosphates regardless the contamination level of the studied soils. No clear effects of calcium phosphates on the microbial and fungi communities were detected. In contrast, results indicated relationships between the physicochemical parameters of soils, their contamination level and the composition of fungal communities. Indeed, for one of the soils studied, calcium could limit the transport of nutrients, causing an increase in fungi to promote again the transfer of nutrients. Surprisingly, the phytoavailability of Pb increased in the most contaminated soil after adding dicalcium phosphate and the mixture of phosphates whereas a slight decrease was highlighted for Cd and Mn. Although minor changes in the phytoavailability of potentially toxic metals were obtained using calcium phosphates, the ability of ryegrass to accumulate Zn and Ca (up to 600 and 20,000 mg kg−1, respectively) make possible to qualify this plant as a bio ‘ore’ resource.