Poly(b-amino ester) networks are gaining attention as a scaffold material for tissue engineering applications where it is important to have tailorable degradation rate and elastic modulus. The objective of this work is to characterize and understand the relationships between chemical structure, polymerization, thermo-mechanical properties, and degradation in poly(b-amino esters) networks. The networks were synthesized from a primary amine with systematically varied molar ratios and chemical structures of diacrylates. Fundamental trends were established between the chemical structure, conversion during polymerization, macromer molecular weight, rubbery modulus, and degradation rate. The thermomechanical properties were dependent upon both polymerization steps. The rubbery modulus was tailorable over a range of several MPa by changing molar ratio and diacrylate molecular weight. The degradation rate ranged from hours to months depending upon the composition. Select chemical structures showed degradation rate independent of modulus. This work provides a basis for designing poly(b-amino esters) networks with specific thermo-mechanical properties and degradation rates for biomedical scaffolds.