High concentrations of soluble orthophosphate, magnesium and potassium are released during anaerobic digestion of biological phosphorus removal (BPR) sludge. This research was undertaken to investigate the effects of phosphorus enrichment on digester performance, metal and phosphorus speciation. High concentrations of soluble PO4-P (> 250 mg/l) were found to have a retarding effect on anaerobic digestion, reducing the rate of volatile solids digestion and methane production in comparison to control digesters. This was found to be reversible after a period of time, which was related to the amount of PO4-P added to the digesters, higher concentrations of PO4-P requiring more time for digester recovery. Addition of magnesium and potassium to the digesters, together with PO4-P, reduced the inhibitory effect of phosphorus enrichment but these digesters still showed lower rates of volatile solids digestion and methane production in comparison to the control digesters. Phosphorus enrichment resulted in extensive precipitation of calcium, magnesium and manganese, markedly reducing the soluble and easily available fractions of these metals. Other trace metals such as copper, zinc, chromium, nickel and cobalt actually showed increased levels of solubility as a result of phosphorus enrichment. This was thought to be caused by high levels of soluble organic carbon in the phosphorus-rich anaerobic digesters, which acted as organic ligands for metal complexation.