We investigated the physical properties and tooth-whitening effect of polymeric tooth-whitening compositions based on orally acceptable polymers, polyvinyl acetate (PVAc), ethyl cellulose (EC), and polyvinyl pyrrolidone. The tooth-whitening composition was prepared with hydrogen peroxide (H2O2) as a tooth-bleaching agent and an orally acceptable polymer through simple mixing and stirring in ethyl alcohol. PVAc and EC polymers showed non-erosive features and sustainable polymeric matrices in a similar oral environment. In particular, non-erosive PVAc polymer exhibited excellent adhesive and flexible film matrix on bovine teeth. PVAc-H2O2 tooth-whitening composition presented a residual H2O2 and an overall color change value (ΔE*) of 26.5% and 16.54%, respectively. The non-erosive polymeric composition is expected to improve tooth-whitening efficacy in various oral products.