Liquid organic hydrogen carriers (LOHCs), such as methanol and formic acid, offer a reliable solution for the challenges associated with transporting and storing gaseous hydrogen. However, the current industrial LOHCs are costly and in limited supply due to complex synthesis methods involving gasification and Fischer-Tropsch synthesis. An alternative approach utilizing efficient pyrolysis methods can convert biomass into substances that mimic LOHCs, making them a promising avenue for hydrogen storage. Compounds with a high hydrogen content, including glycolaldehyde, acetic acid, and acetol, hold potential as effective LOHCs. This study seeks to assess how the specific properties of biomass impact the resulting products and target molecules, focusing on identifying the primary sources of LOHC compounds. The experimental results indicate that glycolaldehyde primarily originates from cellulose, while acetic acid is mainly derived from hemicellulose. Acetol is produced from both cellulose and hemicellulose. At a pyrolysis temperature of 500 °C and a particle size of 0.38–0.83 mm, corn cob yields a higher quantity of glycolaldehyde, acetic acid, and acetol (107 mg/g) compared to rice husk (85.6 mg/g) and pine (68.9 mg/g) due to its significant cellulose and hemicellulose content. Notably, the primary sources of these hydrogen storage molecules during pyrolysis are the initial biomass pyrolysis products rather than secondary reactions.