Printed circuit boards (PCB) are one of the most challenging fractions of e-waste in terms of material recycling and energy recovery. In this study, pyrolysis of PCBs in inert and steam atmosphere has been investigated as a valuable alternative for energy recovery of the organic fraction with simultaneous recycling of metals. The decomposition of two different PCB fractions has been investigated by means of thermogravimetric analysis (TGA) and lab scale pyrolysis experiments in steam and nitrogen atmospheres. The composition of the gas obtained from the pyrolysis experiments was strongly influenced by the reactive atmosphere. The characterization of the solid residue by X-ray Powder Diffraction (XRD) and scanning electron microscopy (SEM) showed high influence of steam to the migration of the antimony in the produced vapors.