Abstract Orange Peel Waste (OPW) is a widely produced residue whose management is complicated by its physical and chemical properties. Anaerobic digestion (AD), which is commonly used for the treatment and exploitation of many biodegradable wastes, is inefficient on OPW due to the presence of essential oils (mainly d -Limonene) as well as the low pH, which cause the process to be unstable. Here we explore the effect of alkaline pre-treatment of OPW and of the addition of granular activated carbon (GAC) and Zero Valent Iron (ZVI) in improving AD in two semi-continuous reactors at a laboratory scale. The addition and pre-treatment of ZVI/GAC were shown to help process stability up to a loading of 3 kgVS·m−3·d−1 and to increase methane production even at a sub-optimal pH. The investigation of the bacterial community, by high-throughput sequencing, has also increased our insight on their involvement in AD in the presence of ZVI, including its biotic oxidation. In addition, direct interspecies electron transfer was shown to play a role in the reactor supplemented with ZVI.