Abstract: Poly(cyclic acetal)s, methods of making same, and uses of same. The poly(cyclic acetal)s may have a number average molecular weight (Mn) of 10 to 3000 kiloDaltons (kDa) and over 50% of the chain ends may exclude hydroxyl groups. The poly(cyclic acetal) may be a homopolymer or copolymer(s) of poly(1,3-dioxolane) (PDXL). The poly(cyclic acetal)s may have one or more or all of: a thermal stability (Td,5%) of 337° C. to 392° C.; a thermal stability of (Td.50%) of 377° C. to 462° C.; or an Arrhenius activation energy (Ea) of 85.0 kJ/mol with 2 mol % of strong acid (e.g., pKa less than or equal to 4). Methods of polymerizing poly(cyclic acetal)s may comprise reacting cyclic acetal monomers with either Lewis acid catalysts and haloalkyl ether initiators or organic cation salt catalyst(s) and proton traps. Methods of chemically recycling poly(cyclic acetal)s into cyclic acetals may react poly(cyclic acetal)s with strong acids.