The application of frontal polymerization to additive manufacturing has advantages in energy consumption and speed of printing. Additionally, with frontal polymerization, it is possible to print free-standing structures that require no supports. A resin was developed using a mixture of epoxies and vinyl ether with an iodonium salt and peroxide initiating system that frontally polymerizes through radical-induced cationic frontal polymerization. The formulation, which was optimized for reactivity, physical properties, and rheology, allowed the printing of free-standing structures. Increasing ratios of vinyl ether and reactive cycloaliphatic epoxide were found to increase the front velocity. Addition of carbon nanofibers increased the front velocity more than the addition of milled carbon fibers. The resin filled with carbon nanofibers and fumed silica exhibited shear-thinning behavior and was suitable for extrusion-based printing at a weight fraction of 4 wt %. A desktop 3D printer was modified to control resin extrusion and deposition with a digital syringe dispenser. Flexural properties of molded and 3D-printed specimens showed that specimens printed in the transverse direction exhibited the lowest strength, likely due to the presence of voids, adhesion issues between filaments, and preferential carbon nanofiber alignment along the filaments. Finally, free-standing printing of single, angled filaments and helical geometries was successfully demonstrated by coordinating ultraviolet-based reaction initiation, low air pressure for resin extrusion, and printing speed to match front velocity.