The impetus for developing analytical methods for phenolic compounds in natural products has proved to be multifaceted. Hundreds of publications on the analysis of this category of compounds have appeared over the past two decades. Traditional and more advanced techniques have come to prominence for sample preparation, separation, detection, and identification. This review provides an updated and extensive overview of methods and their applications in natural product matrices and samples of biological origin. In addition, it critically appraises recent developments and trends, and provides selected representative bibliographic examples.