Frontal polymerization (FP) provides a transformative platform for material manufacturing, leveraging the local heat generated from an exothermic polymerization to propagate an advancing reaction front directly converting monomer into polymer material. The energy efficient, rapid, and scalable nature of FP position it as a pivotal technology for materials synthesis and fabrication via reactive processing. Specifically, the use of ring-opening metathesis polymerization (ROMP), a chain-growth polymerization that relies on the opening of strained cyclic olefins, has shown great promise in the synthesis of high-performance thermoplastic and thermosetting materials (characterized by lightweight, high strength, and resistance to chemicals and high temperatures) and fiber-reinforced polymer composites for industrial applications. While the versatility of ROMP allows for the creation of a wide range of customizable polymers, the potential of frontal ROMP (FROMP) for manufacturing thermoplastics and thermosetting materials remains largely untapped due to the limited range of known suitable monomers. The prominent monomers in FROMP are formed through Diels-Alder (DA) reactions utilizing cyclopentadiene (CPD) to form norbornene-based reactive groups (Figure ). Bio-sourced furan compounds serve as an alternative to petroleum-sourced cyclopentadiene (CPD) for producing ROMP monomers. These furan-based monomers distinguish themselves by their unique physical properties (e.g., boiling point), polymerization kinetics, and the distinct microstructures, thermomechanical, and thermooxidative behaviors of the resulting polymers, compared to those derived from CPD. The broad chemical space accessible with furan-based monomers enables extensive tuning of material properties, offering a stark contrast to the limited options available with CPD-based systems. Herein, we present the identification and reactive processing of furan-derived monomers to produce high-performance polymeric materials via FROMP (Figure ). Initial computational screening suggested that DA products of furans with benzynes are promising monomers, as they not only resist retro-DA processes, but also maintain the necessary ring strain to propel FP. Our experimental findings affirm the successful polymerization of HENs via FROMP and illustrate that modifications in substituents can modulate the physical attributes of monomers, reaction kinetics, and the characteristics of the resulting materials. The practical application of this monomer class is indicated in the 3D printing and the generation of gradient materials, which exhibit spatially varied properties. and enthalpy changes of ring-opening metathesis were calculated with DFT at the wb97xd/def2tzvp level of theory. D. Expanded screening results of monomers derived from benzyne dienophiles and furans with varying methyl substitution as dienes. Substitutions are in the 2and 5-position of the furan.