Phenolics are a large group of plant compounds that have been associated with protective health effects against several chronic diseases due to their potential antioxidant, anti-inflammatory, and anticarcinogenic properties. Consequently, in nutritional epidemiology it is essential to make an accurate assessment of phenolic exposure to evaluate their protective activities against human diseases. Self-reported questionnaires and biomarkers are the two main methods used for estimating dietary phenolics. Despite the limitations of self-reported methods, they are still an acceptable and useful measure. Meanwhile, nutritional biomarkers provide an alternative, more accurate measure, but they are expensive, and to date there are few validated biomarkers of phenolic intake. Nowadays, new analytical techniques, using both targeted and untargeted metabolomic approaches, play an important part in the rapid increase in the understanding of phenolic bioavailability and, consequently, have provided new potential biomarkers in small trials. In the near future, these dietary biomarkers should be tested in large epidemiological studies. Furthermore, the use of two independent measures-questionnaires and biomarkers-together provides a more thorough analysis of true phenolic exposure. Indeed, the challenge in the long term is to combine the information from biomarkers and self-reported questionnaires to clarify the relationship between dietary phenolics and disease.