We report a series of poly(ester amide)s (PEAs) synthesized by organocatalytic ring-opening polymerization (ROP) of N-acylated-1,4-oxazepan-7-one (OxP) monomers, produced from Nacylated-4-piperidones using the Baeyer−Villiger oxidation reaction. The ROP of OxPs, conducted in CH2Cl2 at room temperature with benzyl alcohol as initiator and TBD/TU (1,5,7-triazabicyclo[4.4.0]dec5-ene/thiourea) as a binary organocatalytic system, revealed a controlled/living character. The thermodynamics of the ROP highly depends on the N-acylated substituent of monomers, with the following reactivity order: OxPPh > OxPMe > OxPPr > OxPBn. Based on NMR results, it seems that our system follows the hydrogen bonding bifunctional activation mechanism. All intermediates and final products were characterized by NMR, MALDI-TOF MS, SEC, and DSC techniques. All poly(N-acylated-1,4-oxazepan-7-one) (POxP) polymers are amorphous with different glass transition temperatures (Tg), depending on the N-acylated substituent (Tg: −2.90 to 43.75 °C). Among the synthesized polymers, only POxPMe was water-soluble and it degraded much faster than polycaprolactone in an aqueous phosphate buffer saline solution (pH = 7.4). Therefore, poly(N-acylated-1,4-oxazepan-7-one)s are potential biodegradable alternatives to poly(2-oxazoline)s.