Degradable and recyclable biobased materials offer a sustainable paradigm shift from petrochemical plastics. However, their industrial viability often depends on developing a simple, material-efficient synthetic approach. Here, we report a series of peach gum polysaccharide (PGP)-based vitrimers containing dynamic acetal bonds. These vitrimers were synthesized via a one-step curing process involving a catalyst-free Markovnikov addition reaction between PGP and tri(ethylene glycol) divinyl ether (TEGDVE), with no small molecule emissions. The results demonstrate that the mechanical and thermal properties of these PGP-based acetal vitrimers can be tuned by adjusting the TEGDVE content. Stress relaxation analysis and three-cycle reprocessing experiments confirm the dynamic nature of the networks. Notably, the materials retain mechanical integrity after multiple processing cycles, demonstrating robust dynamic properties. The PGP-based acetal vitrimers exhibit degradation in a biobased citric acid solution, attributed to the decomposition of acetal bonds in their networks. The vitrimers show remarkable scavenging capacity, achieving an ∼92% 2,2-diphenyl-1-picrylhydrazyl (DPPH) inhibition rate. Moreover, these PGP-based acetal vitrimers were evaluated for fruit preservation applications. In cherry shelf life extension trials, they demonstrated a higher preservation efficacy compared to commercial polyethylene films, achieving a 20% decay reduction at room temperature over 10 days.