5-Hydroxymethyl-2-furfural (5-HMF), derived from biomass, is a versatile precursor for various chemicals, including pharmaceuticals, biofuels, plastics, and polymers. This study focuses on synthesizing aromatic vinyl monomers from 5-hydroxymethyl-2-vinylfuran (5-HMVF). Initial steps involve a high-yield Wittig synthesis from 5-HMF, resulting in a 95% yield. Enzymatic synthesis using immobilized CAL-B (iCALB) yields 5-HMVF acetate, n-butyrate, and benzoate in quantitative yields and demonstrates effective enzyme reuse. An alternative TEMPO oxidation route produces 5-vinylfuran-2-carbaldehyde (5-VFA) with a 61% yield, which is further converted to E- and Z-5-vinylfuran-2-carboxime (5-VFO) and subsequently to 5-vinylfuran-2-carbonitrile (5-VFN) via chemocatalytic dehydration. Biocatalytic dehydration of E- and Z-5-VFO to the corresponding nitriles is performed using different aldoxime dehydratases (Oxd) in water as a sustainable solvent. Polymerization of all monomers yields characterized polymer products analyzed by TGA, DSC, SEC, and FTIR spectroscopy.