Trace detection of polycyclic aromatic hydrocarbons is reported in this work on dithiocarbamate calix[4]arene functionalized Ag nanoparticles by using surface-enhanced Raman scattering (SERS). SERS spectra informed about the existence of the pollutant by measuring its characteristic fingerprint vibrational features. In addition, SERS revealed important structural information from both the host and the analyte which was crucial to understand and deduce the host-guest interaction mechanism. The effectiveness of this system was checked for a group of PAHs: pyrene, benzo[c]phenanthrene, triphenylene, and coronene. From the analyzed results, the affinity constants and the limit of detection were deduced for each pollutant.