Green tea (GT) derived epigallocatechin gallate (EGCG) is a commonly used nutraceutical for its antioxidant activity. Caffeine is the second major component and interferes with extraction of EGCG. On-column decaffeination was optimized to enable selective enrichment of EGCG, though less retained than caffeine. EGCG recovery and loss in caffeine were determined using RP-HPLC. Results indicated a significant improvement in caffeine removal and EGCG recovery. The SPE-HPLC protocol represents a model for an efficient and economic approach for improving dynamic capacity, selectivity, and sensitivity towards less retained analytes. This is particularly important for analysis of inherently complex samples of nutraceutical products.