Plastics are a major environmental concern, not only because of their uncontrolled dispersion in the environment, but also because of their release of chemical additives, such as phthalates (PAEs), particularly in water bodies. Key land–water interfaces, such as coastal zones, has always represented a complex and dynamic nexus for plastic pollution, as they are sites often densely populated, with major pollution sources. The Mediterranean basin, for example, is known to be a global hotspot of plastic waste, with a microplastic concentration approximately four times greater than the North Pacific Ocean. However, differently from the overviewed issue of plastic litter and microplastics, the occurrence, distribution, and impact of PAEs on the abiotic and biotic compartment of marine ecosystems of the Mediterranean area have still not been reviewed. Hence, this review provides an introductory section on the plastic pollution issue and its close relationship, not only with microplastics, but also with the leaching of toxic PAEs. To follow, the most relevant analytical approaches for reliably assessing PAEs in abiotic and biotic marine matrices are discussed. The analysis of the main anthropogenic sources of PAEs, their occurrence and spatiotemporal trends in the Mediterranean Sea is conducted. Finally, the potential correlation between PAE pollution and the abundance of microplastics are critically examined to evaluate their effectiveness as tracers of microplastic pollution.