The molecular structure of the lubricating oil highly influences the properties of materials, and the construction of long hydrocarbon structures with highly symmetrical branches is quite challenging. In this work, the efficient coupling of modular molecules (furan, furfural, and aliphatic aldehyde) to C30–C36 starfish-type polyfuran-ring compounds (78% mass yield) was successfully synthesized using a one-pot method at atmospheric pressure, while functionalized SH-containing porous solid phosphate (P/PMO-SH) catalysts were designed and used to catalyze multistep C–C chain alkylation reactions with high spatial site resistance. The in situ introduction of −SH functional groups into P/PMO facilitates the high dispersion of phosphoric acid due to the high specific surface area and well-developed pore structure of the support. In situ infrared experiments provided additional evidence for the promotion of reactant molecule adsorption by sulfhydryl functional groups. Contact angle experiments supported the enhancement of lipophilicity of the catalysts due to these functional groups. The biolubricants produced through Pd/Nb2O5-catalyzed hydrodeoxygenation exhibit high symmetrical branching and demonstrate performance comparable to that of fully synthetic PAO 4 lubricants commercially available, indicating significant potentials for applications.Efficient coupling of modular molecules (furans, furfural, and aliphatic aldehyde) to C30−C36 starfish-type polyfuran-ring compounds using a one-pot method at atmospheric pressure to aid the development of bio-lubricants.