Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in soils and sediments, particularly in urbanized environments in which the concentrations of 16 (or so) PAHs are regulated. Distinguishing among the numerous PAH sources is of practical and legal concern and thereby is often an objective of environmental forensic chemistry studies. Studies of prospective sources and impacted soils and sediments that rely upon the 16 U.S. EPA Priority Pollutant PAHs are disadvantaged, as these few compounds generally lack the specificity to distinguish among different PAH sources in the environment. Advances in analytical and interpretive methods over several decades have shown that different PAH sources can be more defensibly distinguished using modified EPA Method 8270 that, among other improvements, measure many other polycyclic aromatic compounds (PACs) that co-occur with the Priority Pollutant PAHs in different sources and in the environment. The PACs include variously-alkylated PAHs and polycyclic aromatic sulfur heterocyclics (PASHs) homologs and individual isomers, which are herein reviewed. Collectively, these PACs provide a higher degree of specificity among PAC sources and can be used to understand the effects of weathering on PAH assemblages. Despite their diagnostic capacity, PACs should not be relied upon at the exclusion of other compound groups (e.g., petroleum biomarkers) in most environmental forensic chemistry studies. In light of these advances, source characterization studies that rely only upon the 16 (or so) Priority Pollutant PAHs warrant considerable caution.