The accumulation of plastic packaging wastes in the natural environment highlights the significance of sustainable alternatives. Paper is widely used as a biodegradable packaging material, but poor mechanical strength, barrier properties, and water resistance limit its utility. Typical paper coating materials applied to overcome such drawbacks, such as polyethylene (PE) and ethylene vinyl alcohol (EVOH), are not desirable for sustainability due to environmental persistence. Here, we report a biodegradable, biocompatible, robust, and high-barrier paper coating strategy using boric acid-crosslinked poly(vinyl alcohol) (PVA). Various crosslinked-PVA solutions were prepared using boric acid (BA) and hydrochloric acid (HCl) as a crosslinker and an acid catalyst, respectively. The solutions were coated onto the Kraft paper (KP) through facile bar coating with epichlorohydrin (ECH) as a binder (henceforth referred to as coated papers). The coated papers (KP-P, KP-PB, KP-PBH) show remarkably improved oxygen (∼0.89 cc m⁻² d⁻¹) and water vapor (∼5.17 g m⁻² d⁻¹) barrier properties as well as tensile strength (∼53.0 MPa) that is retained in moist conditions. The coated papers were significantly mineralized into CO₂ (59.2–81.6% over 111 d) in the simulated marine environment biodegradation test. Depolymerization of polymer chains and surface degradation of coated papers are evidenced via FT-IR and SEM, respectively. The microcosm test revealed that the intensive disintegration of the coated papers is synergistically driven by both biotic and abiotic factors (i.e., mechanical stress). Moreover, the in vitro biocompatibility tests employing human embryonic kidney and mouse embryonic fibroblast cells, and in vivo biocompatibility test with mice suggest that the coated papers are highly biocompatible. This work provides a promising strategy for paper packaging that enhances packaging performance without compromising environmental sustainability.