Eight 4-carboalkoxyvalerolactones (CRVLs), varying in the composition of their alkyl (R) side chains, were synthesized from malic acid and subjected to ring-opening transesterification polymerization (ROTEP) using diphenyl phosphate [DPP, (PhO)2PO2H] as a catalyst. Each CRVL produced a semicrystalline poly(4-carboalkoxyvalerolactone) (PCRVL), and the nature of the R group impacted the thermal transitions of these polyesters. Bulk polymerizations at 70 °C allowed for preparation of high molar mass samples that contained small amounts of branching, as evidenced by 1H NMR spectroscopy, MALDI spectrometry, size-exclusion chromatography, and eliminative degradation. Tensile testing of these lightly branched, high molar mass samples revealed that these polyesters are tough (tensile toughness values up to 88 ± 33 MJ m-3) and have Young's moduli (E) up to 186 ± 13 MPa. The acid- and base-catalyzed hydrolytic degradation of the PCRVLs was quantitatively monitored by using total organic carbon analysis, and the effect of the alkyl chain length on PCRVL hydrolysis rate was determined. Finally, the methyl ester variant of these malic acid-derived thermoplastics is known to be chemically recyclable.