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Due to the limitation of fossil resources and growing demand of polyester market, to synthesize polyesters from sustainable resources has been a common goal of academic and industrial researchers. The synthesis of linear polyester was started from bio-based furfural. Furfural was first converted to 2-furanacrylic acid as a key photoreactive building block for the synthesis of the monomer. Monomer was then prepared by linking two 2-furanacrylic acid molecules with a bifunctional 1,5-pentanediol, which can also be produced from furfural. An important photoreactive crystalline assembly of the monomer was characterized by powder and single crystal X-ray diffraction. The new linear polyester that contains 100% components from biomass-derived chemicals was synthesized by sunlight photoreaction of the preorganized monomer in the solid state in 12 hours. The solvent-free sunlight photoreaction process was monitored by FT-IR and a key intermediate was confirmed by single crystal Xray diffraction. Nanofiber of the linear polyester was observed under TEM., Zhihan Wang * (G) and Qianli Rick Chu Chemistry, University of North Dakota, Grand Forks, ND Support: NSF EPSCoR Award IIA-1355466. Corresponding Author's Email: [...]