Novel branched alternating copolymers poly(styrene-alt-maleic anhydride) (BPSMA) were synthesized through free radical polymerization with styrene, maleic anhydride, and chain transfer monomer, 4-vinyl benzyl thiol. The successful synthesis of BPSMA was confirmed by a triple detection system including gel permeation chromatography, multiangle laser light scattering, and differential viscosity detectors, as well as thermal analysis (differential scanning calorimetry). This methodology proposes good prospects for scaling-up and thereby offers a wide range of branched alternating copolymers at low cost.