LTTMs are combinations of hydrogen bond donors (HBDs) and hydrogen bond acceptors (HBAs) as a new class of green solvents which aim to overcome the limitation of ionic liquids while sharing some of their advantages. The materials used as HBDs were malic acids extracted from cactus, papaya, and luffa cylindrica while HBAs were L-proline, Lhistidine, glycine, and choline chloride, all of which existed naturally in living organisms or plants. Compatibility of different combinations of HBD and HBA to form LTTMs and varying their molar ratio were the subjects of interest in this project. A biopolymer solubility test was carried out on all LTTMs to identify the best performed LTTM and utilize it in oil palm empty fruit bunch biomass pretreatment. For LTTMs synthesis, only histidine was incompatible with malic acid. The solubility screening test showed that combination of cactus and proline with a molar ratio of 1: 1 (CP 1: 1) is the most effective LTTM in dissolving lignin (12.87 wt), followed by luffa cylindrica : proline 1: 1 (11.53 wt). FTIR analysis was carried out and proved the existence and formation of a hydrogen bond within the solvent structure. The most critical disadvantage of LTTMs was the thermal instability due to its weak hydrogen bonding. CP 1: 1 showed the similar result in biomass pretreatment to the biopolymers solubility screening test, which is around 12 wt of lignin solubility. This work provides an alternative method of biomass pretreatment for lignin extraction. © 2018 by Nova Science Publishers, Inc. All rights reserved.