This study investigates the selective fractionation of lignin with uniform structures and lower molecular weight. Lignin solubilization was first performed using a solution of acetic acid (AA) and hydrogen peroxide (HP) (4:1, (v/v)) to form peracetic acid (PAA), which is a strong oxidant. After the PAA-induced solubilization that occurred at 80°C, totally soluble lignin was extracted by ethyl acetate (EA) and divided into organic- and water-soluble fractions. The EA fraction was then fractionated by open-column using three solutions (chloroform-ethyl acetate, methanol, and water) sequentially. With an increase in the solvent polarity during the fractionation step, the molecular weight of the lignin-derived compounds in the fraction increased. Remarkably, some lignin fractions did not have aromatic structures. These fractions were identified as carboxylic acid-containing polymers like poly-carboxylates. These results conclude that the selective production of lignin-derived polymers with specific molecular weight and structural characteristics could be possible through open-column fractionation.