Geopolymer enhances mechanical properties with polyvinyl alcohol (PVA) fibers, but there has been limited research exploring low PVA fiber dosages for mechanical properties in 3D printing or shotcrete. This study experimentally investigated slag and fly ash-based geopolymer mixtures reinforced with 0.1%, 0.15%, and 0.2% PVA fiber by volume as well as a control group without PVA fibers. These mixtures were prepared using fly ash, quartz sand, slag powder, silica fume, and an aqueous sodium silicate solution as the alkali activator, with the addition of PVA fiber to enhance composite toughness. The mechanical properties of the composites, encompassing dog-bone tensile properties, cubic compressive strength, bending and post-bending compressive strength, and prism compressive properties, were evaluated. Significantly, specimens with 0.15% PVA fibers exhibited optimal performance, revealing a notable 28.57% increase in tensile stress, a 36.45% surge in prism compressive strain, and a 47.59% rise in tensile strain compared to fiber-free specimens. Furthermore, environmental scanning electron microscopy observations were employed to scrutinize the microscopic mechanisms of composites incorporating PVA fibers, slag, and fly ash. In comparison to fiber-free specimens, prism compressive specimens with 0.15% PVA fibers demonstrated a 27.17% increase in post-cracking loading capacity, a 44.07% increase in post-cracking ductility, a 50.00% increase in peak strain energy, and a 76.36% increase in strain energy ratio.