Crude polysaccharides and proteins extracted from algae were chosen as model materials to investigate the hydrothermal liquefaction (HTL) characteristics and pathways of low-lipid algae. Liquefaction behavior of the two individuals and their binary mixtures with different mass ratios were evaluated under different temperatures. Formation pathways of bio-oil from crude polysaccharides/proteins were proposed. Results showed that polysaccharides had a small contribution to bio-oil (<5%) and approximately 60% distributed in aqueous phase, while proteins played a crucial role on bio-oil formation (maximum 16.29%). Bio-oil from polysaccharides mainly contained cyclic ketones and phenols and from proteins composed of pyrazines, pyrroles and amines. Interaction between polysaccharides and proteins forming polycyclic nitrogenous compounds had a negative effect on bio-oil yield at 220 and 260°C. However, their further decomposition caused increase of bio-oil yield at 300°C. Mixture liquefaction obtained the highest higher heating value (HHV) of bio-oil and energy recovery than polysaccharides/proteins liquefaction at 300°C.