Design and preparation of gels with excellent mechanical properties has garnered wide interest at present. In this paper, preparation of polyvinyl alcohol (PVA)-tannic acid (TA) gels with exceptional properties is documented. The crystallization zone and hydrogen bonding acted as physical crosslinkages fabricated by a combination of freeze-thaw treatment and a tannic acid compound. The effect of tannic acid on mechanical properties of prepared PVA-TA gels was investigated and analyzed. When the mass fraction of PVA was 20.0 wt% and soaking time was 12 h in tannic acid aqueous solution, tensile strength and the elongation at break of PVA-TA gel reached 5.97 MPa and 1450%, respectively. This PVA-TA gel was far superior to a pure 20.0 wt% PVA hydrogel treated only with the freeze-thaw process, as well as most previously reported PVA-TA gels. The toughness of a PVA-TA gel is about 14 times that of a pure PVA gel. In addition, transparent PVA-TA gels can effectively prevent ultraviolet-light-induced degradation. This study provides a novel strategy and reference for design and preparation of high-performance gels that are promising for practical application.