A highly efficient extraction of caffeine from fresh green tea leaves by using water as the extraction solvent, DM310 macroporous as a selective adsorbent and ethyl acetate as a desorption solvent was developed. This desorption solvent is a new bio-renewable agrochemical solvent, naturally produced by fermentation from corn derived feedstock, which has been recently considered as a very suitable and environmental benign solvent for food industrial applications. The optimum conditions to extract caffeine from Phu Tho province’s fresh green tea leaves determined maximum achieved extraction efficiency of caffeine with water using selective absorbent was obtained at 90 oC for 10 min with fresh green tea leaves/water ratio of 1/5 g/ml. The caffeine extraction efficiency achieved 86.7% with high purity.Keywords caffeine, DM310 macroporous, ethyl acetate, high purity, green solvent