Researchers have been chasing plastics that can automatically and fully degrade into valuable products under natural conditions. Here, we develop a series of water‐degradable polymers from the first reported fast and selective cationic copolymerization of formaldehyde (B) with cyclic anhydrides (A). In addition to readily accessible monomers, the method is performed at industrially relevant temperatures (~100 °C), takes tens or even minutes, and uses common acid as the catalyst. Interestingly, such polymers possess tunable AB/ABB‐type repeating units, which are considered to be thermodynamic and kinetic products, respectively, resulting in low carbon content ([O]:[C] up to 1:1). Notably, the polymers can completely degrade to valuable diacids within 150 days in water at ambient temperature owing to the incorporation of carboxyl terminals and acid‐responsive acetal units. By washing with aqueous sodium carbonate, the polymers are relatively stable over several months.