In this study, an ID-GC-TOF-MS method was developed and validated for polycyclic aromatic hydrocarbons (PAHs) by spiking solutions onto thermal desorption tubes using calibration solution loading ring (CSLR) apparatus and sweeping them by the aid of air stream. Once the method was developed and validated, the effect of other compounds found in biogas and biomethane was investigated by the same methodology used in method development by using a gravimetrically prepared biogas mixture consisting of 45% methane, 40% carbon dioxide and 15% nitrogen. There are standard reference methods for measurements of PAHs in air but there was no available standard method for PAHs in biogas and biomethane yet. This study provides a basis for the future studies to develop a standard method. Data obtained through this study showed that present method is not affected by the compounds found in biogas that are not present in other matrices such as ambient air.