Long-chain hyperbranched polyesters (LHBPx, x = 1, 2, 3) with varying lengths of branched chains were synthesized through a thiol-ene click reaction. Subsequently, LHBPx was incorporated into PA4 via the solution method to prepare a LHBPx/PA4 polymer blend, aiming to address the limitations of PA4, such as its narrow thermal processing window (△T = T