Caffeine

Having a triple espresso iced mocha as I type this :-P

Trivia: Glycogen is the principal fuel for muscles and exhaustion occurs when it is depleted. A secondary fuel, which is much more abundant, is fat. As long as there is still glycogen available, working muscles can utilize fat. Caffeine mobilizes fat stores and encourages working muscles to use fat as a fuel. This delays the depletion of muscle glycogen and allows for a prolongation of exercise. The critical time period in glycogen sparing appears to occur during the first 15 minutes of exercise, where caffeine has been shown to decrease glycogen utilization by as much as 50%. Glycogen saved at the beginning is thus available during the later stages of exercise. (Source)