The transition toward sustainable polymer materials necessitates overcoming the end-of-life recycling limitations inherent to traditional thermosets. Covalent adaptable networks (CANs) based on poly(β-amino esters) (PBAEs) offer a highly promising solution by uniquely exhibiting mechanistic duality, seamlessly transitioning between associative transesterification at moderate temperatures and dissociative aza-Michael exchange at elevated temperatures. This study reports the design, synthesis, and characterization of novel, structurally tunable, and catalyst-free PBAE CANs. A customized Michael acceptor, mono-methacrylate triethanolamine (MATEOA), was synthesized to provide built-in network branching and internal hydrogen-bond catalysis. Structural characterization of the synthesized MATEOA revealed a product dispersion mostly composed of tris-MATEOA (70%), with the mono-substituted fraction comprising 23% of the mixture.