As many soils are unable to supply sufficient amounts of phosphorus (P) to plants, P availability is often a growth-limiting factor. Literature shows that levels of readily available P can be considerably higher in earthworm casts than in the surrounding bulk soil, possibly resulting in increased plant P uptake. However, the underlying mechanisms through which this increase of readily available P occurs are unclear. In a greenhouse pot experiment with annual ryegrass (Lolium multiflorum) on a soil with low P availability, we tested whether the presence of the anecic earthworm Lumbricus terrestris resulted in increased grass growth and P uptake and explored the possible mechanisms behind such an effect. During the pot experiment, earthworm casts were collected and analysed for water-extractable P as well as for most other relevant ions. The earthworm's presence significantly increased grass yield from 9.80 to 10.80 g dry matter per pot (p = 0.044) and P uptake from 6.32 to 8.04 mg per pot (p = 0.002). Due to increased microbial activity, the solution chemistry in the water extracts of the casts was dramatically changed compared to the bulk soil samples. The concentrations of dissolved inorganic P in cast were enhanced by a factor ~ 30–1000 compared to the levels found in bulk soil. The pH in earthworm casts increased from 5.9 to values between 7.4 and 9.0 and the Ca concentrations decreased by about a factor ~ 2-3 compared to bulk soil samples. In addition, there was an increase in dissolved organic carbon (35 mg L− 1 in casts versus 3 mg L− 1 in soil). Surface complexation modelling, using the Charge Distribution model, suggests that, besides an increase in pH, particularly an enhanced interaction of dissolved organic matter with reactive surface of metal (hydr)oxides is likely to be a major driving force for the augmented release of orthophosphate (PO4) via competitive adsorption and desorption. This competition for adsorption sites is an alternative pathway, next to mineralisation of organic matter, through which earthworms can increase soil fertility.