The influence of Zero Valent Iron (ZVI) addition on the potential resource recovery during the anaerobic digestion (AD) of domestic waste sludge is assessed. Potentially recoverable resources analyzed were nutrients such as struvite to recover P, and energy as biogas to recover C. Short term (biochemical methane potential tests, BMP) and long term (AD1, AD2) experiments are conducted using two types of set-up (batch, continuous). Process data (influent, effluent and biogas) is continuously collected and the dry digested sludge is analyzed by XPS. A mathematical model is developed based on a modified version of the Anaerobic Digestion Model No 1 upgraded with an improved physicochemical description, ZVI corrosion, propionate uptake enhancement and multiple mineral precipitation. The results of all experiments show that ZVI addition increases methane production and promotes the formation of siderite (FeCO3) and vivianite (Fe-3(PO4)(2)), which causes changes in the biogas composition (%CH4 versus % CO2) and reduces P release. The model can satisfactorily reproduce the dynamics of AD processes, nutrient release, pH and methanogenesis in AD1. The proposed approach also describes the changes in the overall performance of the process because of ZVI addition in AD2. A model-based scenario analysis is included balancing chemical-ZVI addition and increased methane production/struvite precipitation. This scenario analysis allows concluding that: (a) the improvement of methane production does not compensate the costs of ZVI purchase, and (b) ZVI dramatically decreases the P recovery potential in the digestate of the AD systems. This is the first study to experimentally and mathematically describe the effect of ZVI on biogas production/composition and on the fate of phosphorus compounds, and its potential implications for potential energy and phosphorus recovery in AD systems.