Thermally stable and transparent polymers were synthesized by the sequence-controlled radical copolymerization of N-substituted maleimides (RMIs) with various olefins as well as polyisobutene (PIB) macromonomers. The copolymerization behavior significantly depended on the olefin structures, leading to the formation of AB-alternating and AAB-periodic (2:1 sequence-controlled) copolymers. The sequence-controlled radical copolymerization mechanism was discussed based on the monomer reactivity ratios, which were determined using terminal and penultimate unit models for the copolymerization systems investigated in this study as well as in the literature. The olefin comonomers were classified into several groups according to the copolymerization fashions under the terminal and penultimate unit controls and their conjugated structure and the steric bulkiness of the substituents. The copolymers exhibited excellent thermal properties; the onset temperatures of the resulting copolymers were higher than 300 degrees C, and the glass transition temperature (T-g) values varied over the temperature range of -68 to 210 degrees C, depending on the structure of the N- and alpha-substituents of the comonomer repeating units. The introduction of sterically hindered substituents increased the T-g values, while the introduction of the PIB segments as the side chain of the copolymers resulted in a significant decrease in the T-g value and unique fluidity. The optical and viscoelastic properties of the high-T-g copolymers were investigated.