The growing number of heterogeneous polymeric species that are being synthesized places increasing demands on existing analytical techniques. Although size-exclusion chromatography (SEC) has established itself as a powerful analytical tool, it has its limits when complex polymers, e.g., graft copolymers, must be analyzed. In this case, complementary techniques such as gradient HPLC and liquid chromatography at critical conditions (LCCC) are more favorable. The present study describes the synthesis and analysis of methyl methacrylate-and styrene-grafted epoxidized natural rubber by different chromatographic techniques. The grafting efficiency was evaluated by gradient HPLC under normal and reversed phase conditions. Methyl methacrylate-grafted ENR50 was further analyzed by LCCC, where separation of the rubber and grafted rubber occurred according to chemical composition but was independent of the molar mass of the methyl methacrylate homopolymers. This was followed by the combination of LCCC and SEC, where separation was achieved in two dimensions. Relevant deductions were made of both the chemical composition distribution and the molar mass distribution of the functional groups of methyl methacrylate-grafted ENR50. (C) 2003 Wiley Periodicals, Inc.