The biodegradation of polychlorinated biphenyls (PCBs), formerly applied in technical mixtures called Delor 103, was realized by the white rot fungus Pleurotus ostreatus. Besides the efficiency of degradation the translocation of PCBs into the fruit bodies grown during cultivation on straw were of special interest. The selectivity of PCBs degradation is discussed on the basis of structural features of the individual congeners. The most important structural factors affecting the degradation efficiency are indicated with molecular descriptors. Basic dependences of the degradation efficiency of congeners on their chlorination grade and ortho chlorosubstitution could be proved. Additionally, other structural parameters such as the number and position of non-substituted carbon in the biphenyl molecule also affect the degradation results. Apart from the removal of Delor 103 the translocation of PCB isomers into the fruit bodies growing up during cultivation was observed. The structural features assisting the transport of PCB congeners from the straw substrate colonized with mushroom mycelium (straw/mycelium) to the mushroom fruit bodies are also relevant for the degradation mechanism but act reversely. Among the chlorination grade, structural parameters such as the number of para and adversely positioned chlorines or the number of occupied para and meta positions contribute to an accumulation of individual PCB congeners in the mushrooms. In total, only few PCB amounts (below 0.1% of the initially present PCBs in straw) were transported into the fruit bodies and a dangerous PCB contamination was never reached while the experiment. A combination of accelerated solvent extraction and GC-MS analysis was the analytical basis for the investigation presented.