In the last years, there is great attention paid to the determination of polycyclic aromatic hydrocarbons (PAHs) in different environmental matrices. Extensive reviews on PAHs presence and toxicity were published recently. However, PAHs formation and transformation in the environment lead to the production of PAHs derivatives containing oxygen (O-PAHs), nitrogen (N-PAHs and aazarenes AZA) or sulfur (PASHs) in the aromatic ring. The development of new analytical methods enabled the determination of these novel contaminants. The presence of oxygen, nitrogen, or sulfur in PAHs aromatic rings increased their toxicity. The most common primary sources of PAHs derivatives are biological processes such as microbial activity (in soil, water, and wastewater treatment plants (O-PAHs)) and all processes involving combustion of fuel, coal, and biomass (O-PAHs, N-PAHs, AZA, PASHs). The secondary resources involved i) photochemical (UV light), ii) radical-mediated (OH, NO₃), and iii) reactions with oxidants (O₃, NO_x) (O-PAHs, N-PAHs, AZA). Furthermore, N-PAHs were able to transform to their corresponding O-PAHs, while other derivatives were not. It indicated that N-PAHs are more vulnerable to photooxidation in the environment. 85% of O- and N-PAHs were detected with particle matter below 2.5 μm suggesting their easier bioaccessibility. More than 90% of compounds with four and more aromatic cycles were present in the particle phase in the air. Although the concentrations of N-PAHs or O-PAHs may be similar to PAHs concentration or even 1000 times lower than parent PAHs, PAHs derivatives accounted for a significant portion of the total mutagenicity. The present review is describing the results of the studies on the determination of PAHs derivatives in different environmental matrices including airborne particles, sediments, soil, and organisms. The mechanisms of their formation and toxicity were assessed.