Our computational screening identified DA products of furan and benzynes (i.e., 1,4-dihydro-1,4-epoxynaphthalenes) as ideal candidates due to their resistance to rDA reactions and sufficiently large heats of polymerization. Subsequent experimental investigations revealed that the monomer substitution pattern tunes the FROMP reaction kinetics as well as the resultant polymer material properties. Inclusion of methyl groups on the furan moiety increases the glass transition temperatures and storage moduli of the materials compared to those derived from the unsubstituted parent monomer; additionally, these substituents depress the polymerization rate and degree of polymer chain entanglement. By employing a HEN-based crosslinker, we produced more stable polymers with desirable thermomechanical properties. The resins derived from these HENs were successfully 3D printed using FROMP-DIW. Moreover, the versatility in the physical and mechanical properties of the monomers and the resulting frontally polymerized materials enabled the production of materials with spatially varying material properties. We believe that the HEN-based monomers with their diverse chemistries can help foster the development of high-performance materials suitable for a wide array of applications while maintaining a focus on sustainability and energy-efficiency in manufacturing.