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Characterizing RNA\u2013protein interactions remains challenging, particularly for dynamic or low\u2010abundance complexes. Traditional crosslinking methods, such as UV\u2010254\u00a0nm irradiation and formaldehyde fixation, suffer from low efficiency, poor specificity, and broad reactivity, limiting their utility for high\u2010resolution interactome mapping. Recent advances in genetic code expansion (GCE) and unnatural amino acid (UAA) incorporation now enable chemoselective, site\u2010specific crosslinking chemistries that circumvent these limitations. This review highlights classes of crosslinkable UAAs, including benzophenone\u2010, diazirine\u2010, and aryl azide\u2010based moieties, which have been used for photo\u2010induced covalent capture of RNA\u2013protein interactions. Next\u2010generation modalities, such as acetophenone derivatives, halogenated UAAs, bifunctional UAAs, acyl silanes, diaryl nitrones, and photoactivatable systems further expand the toolkit for photocrosslinking and bioorthogonal labelling. Beyond UV\u2010based approaches, latent bioreactive UAAs and proximity\u2010induced chemistries exploit electrophile\u2013nucleophile substitution and masked acylating agents to enable covalent capture under physiological conditions. Together, these strategies provide unprecedented control over reactivity, temporal resolution and site specificity, advancing RNA\u2010targeted proteomics. 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