Lignin is a renewable source of aromatics with great potential as a substitute for fossil-based phenolic compounds that are used in several material applications. However, the available technical lignins are heterogenic and still structurally not fully understood. This presents hurdles for studies focused on gaining fundamental insights into how materials properties are related to the molecular structure of lignin. In the present study, a novel cyclic extraction process for lignin is more deeply studied to investigate the potential to tailor the chemical and physical properties of lignin. For this purpose, a design of experiment (DoE) approach was adopted as a tool to investigate the effect on the lignin properties of the selected parameters by including linear, quadratic and interaction effects in a multiple linear regression (MLR) model. Molecular characterization techniques included 1D and 2D NMR, SEC and DSC. It was clearly demonstrated that the chemical and physical properties of lignin could be tuned for the cyclic process using the DoE approach, while preserving 66–82% of the commonly known lignin inter-units, substantiating that the cyclic extraction approach offered a decent to excellent level of protection to inter-units when compared to benchmark organosolv and kraft lignin. By manipulation of the extraction conditions, the β-O-4′ content can be tuned between 20 and 35% simultaneously with the content of phenolic and aliphatic hydroxyls. Finally, DSC studies showed T_gs in the range of 150–185 °C which are discussed with respect to the molecular properties of the analysed lignin. Overall, to advance efforts in lignin valorization, a green process to produce a library of well-characterized lignins, tailored with respect to chemical and physical properties by process conditions, is presented.