Poly-beta-alanine (PBA), and its derivatives poly(alpha-methyl-beta-alanine) and poly[N-(3-methoxypropyl-beta-alanine) were synthesized by hydrogen transfer polymerization (HTP). Porous 3 D matrices of poly(3-hydroxybutyrate) (P3HB) reinforced with PBA/its derivatives were obtained via lyophilization and wet electrospinning. However, mechanical properties of the porous matrices prepared by wet electrospinning were found to present superior performance for tissue engineering applications. Cell culture study was performed by using wet electrospun P3HB matrices doped with 10% (w/w) PBA which show better manipulation ability, chemical and mechanical properties. Scaffolds of P3HB-PBA (10% w/w) blend was determined to demonstrate better cell attachment and proliferation compared to the scaffolds of pure P3HB.