Abstract Regioselective enzymatic polycondensation of the bio–based cellulose derived polyol, Triol–citro, and dimethyl adipate using Candida antarctica Lipase B (CaLB) was investigated. A Design of Experiment approach with MODDE® Pro 13 was used to determine important factors in the branching behavior of this polymer, and reactant ratio, temperature, reaction time and enzyme wt % were the studied factors. Multifunctional polyesters with pendant hydroxy groups were synthesized and fully characterized using 2D NMR techniques to determine degree of branching. Branching was minimal, with a maximum of 16 % observed, and monomer ratio, temperature and reaction time were all determined to be significant factors. In this work, M n of up to 13 kDa were achieved, while maintaining degree of branching below 15 %, resulting in a linear polyester with the potential to be further functionalized.