Tree mortality caused by bark beetles has increased in recent decades in both Europe and North America. In a large recent outbreak in central Sweden the bark beetle Polygraphus poligraphus was often found together with the spruce bark beetle Ips typographus in killed trees. To increase the understanding of the aggregation behavior of P. poligraphus we used solid phase microextraction (SPME) to collect volatile organic compounds (VOCs) released from single P. poligraphus males, with and without added females, colonizing Norway spruce stem sections and analyzed the sampled compounds by combined gas chromatography and mass spectrometry (GC-MS). High amounts of terpinen-4-ol, a substance found in the hindguts of P. poligraphus males in earlier studies, were released by colonizing males. The emission of both enantiomers of terpinen-4-ol was monitored by GC-MS over time as the males aged in the absence and presence of females. Single males emitted (R)-(-)-terpinen-4-ol for up to 60 days in high enantiomeric purity but the enantiomeric excess (ee) varied between males, and also for the same individual, over time from 96.3% to 99.3% ee. In the presence of females, males also emitted terpinen-4-ol for up to 50 days but now in lower amounts and with lower enantiomeric purity varying from 67.7% ee to 99.3% ee. Small quantities of other volatile compounds were emitted from the colonizing beetles including cis- and trans-4-thujanol, both of which were previously shown to be present in the hindguts of males. In earlier studies frontalin was found to attract P. poligraphus, but in our study it was not identified among emitted compounds from colonizing beetles.