Fiber-reinforced concrete (FRC) is a promising construction material mainly because of the crack-controlling mechanisms that discrete fibers can impart to inherently brittle concrete. Macrofibers, in particular, have been proven effective for providing post-crack ductility and toughness, while synthetic fibers are a promising solution to avoid corrosion-related durability issues. To assess the performance enhancement provided by macro-synthetic concrete fibers, this study performs flexural tests on FRC beams containing three different types of macro-synthetic fibers. The selected fibers include polypropylene (PP), polyvinyl alcohol (PVA), and alkali-resistant glass (ARG) macrofibers mixed at volume fractions of 0.5%, 1.0%, and 1.5%. Static and dynamic fresh properties are monitored using the vibrating Kelly ball (VKelly) test. Beam specimens are then placed under a third point bending configuration, as per ASTM C1609 Standard, to measure load versus mid-span deflection. Strength and toughness parameters are derived from the load–deflection data to assess the flexural performance of the FRC composite systems under consideration. The parameters of interest include first peak strength (pre-crack flexural strength) and post-crack residual strength and toughness provided by fiber addition. Of the mixtures tested, ARG fiber mixtures show the highest residual strength and toughness values, followed by PP and PVA fiber mixtures. ARG fibers produce the most workable mixtures at all fiber volumes, while PVA fibers show a tendency to encounter dispersion issues at higher volume doses. The outcome of this study is expected to facilitate the selection of fibers by giving insight into their relative contribution to fresh and hardened flexural properties of FRC.