The 4μ-A2B2 star-shaped copolymers containing PS, PI, PtBA, or PAA arms were synthesized by Glaser coupling and multiple polymerization mechanisms (LAP and ATRP), and the target copolymers were well characterized by SEC, MALDI-TOF mass spectra, FT-IR, and 1HNMRin detail. In this paper, the condition of Glaser coupling was largely simplified, and LAP was successfully combined with ATRP mechanism. Our work provided a versatile strategy to 4μ-A2B2 star-shaped copolymers with various compositions.