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Raman spectroscopy is gaining ground in the analysis of microplastics, especially due to its high spatial resolution that allows the investigation of small plastic particles, whose numeric abundance is argued to be particularly relevant in aquatic systems. Here, we aimed at outlining the status of Raman analysis of microplastics from aquatic systems, highlighting the advantages and the drawbacks of this technique and critically presenting tools and ways to effectively employ this instrument and to improve the spectra obtained and their interpretation. In particular, we summarized procedural information for the use of Raman spectroscopy, and we discussed issues linked to fluorescence interference and the analysis of weathered polymers, which may complicate the interpretation of Raman signatures. In this context, a deep understanding of the different plastic polymers and their Raman peaks and chemical fingerprints is fundamental to avoid misidentification. Therefore, we provided a catalog with detailed information about peaks of most common plastic polymers, and this represents, to the best of our knowledge, the first comprehensive resource that systematically synthesized plastic Raman peaks. Additionally, we focused on plastic additives, which are contained in the majority of plastics. These compounds are often intense in Raman scattering and may partly or completely overlie the actual material types, resulting in the identification of additives alone or misidentification issue. For these reasons, we also presented a new R package “RamanMP” that includes a database of 356 spectra (325 of which are additives). This will help to foster the use of this technique, which is becoming especially relevant in microplastic analysis.