This is the first time that the adsorption of binary mixtures of polycyclic aromatic hydrocarbons (PAHs) has been studied. This study was carried out at laboratory scale in an experimental apparatus specially designed for this aim: with gas-phase fluorescence, a new detection procedure was used. Experimental conditions, mainly in terms of temperature (150degreesC) and contaminant concentration (approximately I ppmv), close to the ones observed in energy generation systems, were applied. The PAH adsorption process interpretation was carried out by recording the experimentally obtained breakthrough curves. After the detection parameter optimization, the influence of adsorbate characteristics in the hot gas cleaning of PAH was studied. In this system, the adsorption of 10 binary mixtures of five PAH [naphthalene (Np), fluorene (Fu), phenanthrene (Phe), fluoranthene (Fl), and pyrene (Py)] on an activated carbon was investigated. It was found that the adsorbent efficiency is always determined by the breakthrough of the weakly adsorbed component during its adsorption as pure compound. This efficiency and the equilibrium adsorption capacity, the sum of the adsorption capacity of both compounds, depend on binary mixture components, and as it happened for the pure compounds, microporosity is the main factor that controls the adsorption process. Finally, it was found that the pore volumes filled by the binary mixtures was always similar or lower than the ones filled by the strongly retained binary mixture component as pure compound. This difference mainly depended on the volatility of the weakly retained component.