Polyolefin thermoplastic elastomers (TPE‐Os) are high‐performance polyolefins consisting of both plastic and rubber phases. Compared with other thermoplastic elastomers, the TPE‐Os possess better chemical stability, transparency, re‐processability, and electrical insulation, which renders their broad applications possible. By manipulating chain structures and topologies of the TPE‐Os, differently structured polyolefins with improved thermal and mechanical properties have been developed, including ethylene and α‐olefin random copolymers (POEs), olefin block copolymers (OBCs), comb‐shaped polyolefin elastomers (CPOEs), and dynamically cross‐linked polyolefin elastomers. Herein, we review the synthesis of the POE, OBC, CPOE, and dynamical cross‐linked polyolefin elastomer, including the catalyst systems, polymerization techniques, processes, and kinetic modelling. The characterization of the TPE‐Os and the relationships between the TPE‐O chain structure, aggregated state, and product performance are discussed. The future development of higher‐performance TPE‐Os is envisaged.