The present paper evaluates the efficiency of sustainable activated carbons obtained from the valorization of lignocellulosic waste in removing siloxanes and volatile organic compounds for the purification of anaerobic digester biogas. Pyrolized and non-pyrolized lignocellulosic residues generated in food and wood industries were used as precursor materials to obtain experimental adsorbents by a chemical activation process using several activating agents. The highest porosity was obtained by non-pyrolized residue activated by K2CO3 at 900 °C. The performance of the experimental materials was compared with that of commercial activated carbons in gas adsorption tests of siloxanes (octamethylcyclotetrasiloxane and hexamethyldisiloxane) and volatile organic compounds (toluene and limonene). The waste-based activated carbons developed in this work proved to be more efficient for the removal of both siloxanes and VOCs than the commercial samples in most of the conditions tested. Adsorption capacities correlated with porosity, while the more relevant pore size depends on the adsorbate.