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