Synthesizing hydroxy-functional linear copolymers with high molecular weights (M_n) and low branching degree (Den%) remains challenging, although there has been much headway in the area of functional copolymers. Here, we studied the effect of polymerization methods (one-step or two-step) and solvents (organic solvent: diphenyl ether or ionic liquids: [C_nmim]TF₂N/BF₄/PF₆, n = 2, 4, 6, 8, or 10) on M_n and Den% of copolymers P(OA–GA) (1,8-octanediol adipate (O-A)/glycerol adipate (G-A)). The M_n of P(OA–GA) reached up to 53 937 g mol⁻¹ in two-step in diphenyl ether, and the Den% of glycerol can be controlled within 30%. The physical properties of these copolymers were investigated by contact angles, differential scanning calorimetry (DSC), and in vitro biodegradation. With increasing glycerol content in the polyesters, both hydrophilic properties and degradation properties increased. This system not only facilitates the synthesis of functional polyesters with high molecular weight and low branching, but also expands the possibility of using bio-based monomers to synthesize functional polymers.