In the 70s, reports began to appear of phenolic metabolites of brown algae with the characteristics of tannins; these compounds, initially termed phaeophyte tannins, marine algal polyphenols or polyphloroglucinols, are known as phlorotannins, the youngest group of plant polyphenolics. Despite over 40 years of research in phlorotannins, this area is still in the exponential growth phase; however, several reviews have appeared, primarily concerning their biological activity. This review focuses on techniques for the extraction, isolation and chromatographic purification of approximately 150 phlorotannins during these four decades. Due to the high structural diversity of these polyphenols and the difficulty of classification, these topics are also reviewed: structural diversity and classification, extraction and preparative chromatography, thin-layer chromatography, and analytical high-performance liquid chromatography (HPLC) and HPLC-mass spectrometry. These techniques have primarily been used for separation monitoring and qualitative profiles, and not too many reports have been published on the development of quantification or quality control.