Phenolic compounds are highly valuable food components due to their potential utilisation as natural bioactive and antioxidant molecules for the food, cosmetic, chemical, and pharmaceutical industries. For this purpose, the development and optimisation of efficient extraction methods is crucial to obtain phenolic-rich extracts and, for some applications, free of interfering compounds. It should be accompanied with robust analytical tools that enable the standardisation of phenolic-rich extracts for industrial applications. New methodologies based on both novel extraction and/or analysis are also implemented to characterise and elucidate novel chemical structures and to face safety, pharmacology, and toxicity issues related to phenolic compounds at the molecular level. Moreover, in combination with multivariate analysis, the extraction and analysis of phenolic compounds offer tools for plant chemotyping, food traceability and marker selection in omics studies. Therefore, this study reviews extraction techniques applied to recover phenolic compounds from foods and agri-food by-products, including liquid–liquid extraction, solid–liquid extraction assisted by intensification technologies, solid-phase extraction, and combined methods. It also provides an overview of the characterisation techniques, including UV–Vis, infra-red, nuclear magnetic resonance, mass spectrometry and others used in minor applications such as Raman spectroscopy and ion mobility spectrometry, coupled or not to chromatography. Overall, a wide range of methodologies are now available, which can be applied individually and combined to provide complementary results in the roadmap around the study of phenolic compounds.