Carbohydrate and fat are the main substrates utilized during prolonged endurance-type exercise. The relative contribution of each is primarily determined by the intensity and duration of exercise, along with individual training and nutritional status. During moderate-to-high intensity exercise, carbohydrate represents the main substrate source. As endogenous carbohydrate stores (primarily in liver and muscle) are relatively small, endurance-type exercise performance/capacity is often limited by endogenous carbohydrate availability. Much exercise metabolism research to date has focused on muscle glycogen utilization with little attention to the contribution of liver glycogen. ¹³C magnetic resonance spectroscopy permits direct, non-invasive measurements of liver glycogen content and has increased understanding of the relevance of liver glycogen during exercise. In contrast to muscle, endurance-trained athletes do not exhibit elevated basal liver glycogen concentrations. However, there is evidence that liver glycogenolysis may be lower in endurance-trained athletes compared to untrained controls during moderate-to-high intensity exercise. Liver glycogen sparing in an endurance-trained state may therefore partly account for training-induced performance/capacity adaptations during prolonged (>90 min) exercise. Ingestion of carbohydrate at a relatively high rate (>1.5 g/min) can prevent liver glycogen depletion during moderate-intensity exercise, independent of the type of carbohydrate (e.g. glucose vs sucrose) ingested. To minimize gastrointestinal discomfort, it is recommended to ingest specific combinations or types of carbohydrates (glucose plus fructose and/or sucrose). By co-ingesting glucose with either galactose or fructose, post-exercise liver glycogen repletion rates can be doubled. There are currently no guidelines for carbohydrate ingestion to maximize liver glycogen repletion.