It has been reported that green tea has a thermogenic effect, due to its caffeine content and probably also to the catechin, epigallocatechin-3-gallate (EGCG). The main aim of the present study was to compare the effect of a mixture of green tea and Guarana extracts containing a fixed dose of caffeine and variable doses of EGCG on 24 h energy expenditure and fat oxidation. Fourteen subjects took part to this randomized, placebo-controlled, double-blind, cross-over study. Each subject was tested five times in a metabolic chamber to measure 24 h energy expenditure, substrate oxidation and blood pressure. During each stay, the subjects ingested a capsule of placebo or capsules containing 200 mg caffeine and a variable dose of EGCG (90, 200, 300 or 400 mg) three times daily, 30 min before standardized meals. Twenty-four hour energy expenditure increased significantly by about 750 kJ with all EGCG–caffeine mixtures compared with placebo. No effect of the EGCG–caffeine mixture was observed for lipid oxidation. Systolic and diastolic blood pressure increased by about 7 and 5 mmHg, respectively, with the EGCG–caffeine mixtures compared with placebo. This increase was significant only for 24 h diastolic blood pressure. The main finding of the study was the increase in 24 h energy expenditure with the EGCG–caffeine mixtures. However, this increase was similar with all doses of EGCG in the mixtures.