In our previous work, we developed new PBS-DLS copolymers modified with PEG and by changing the segmental compositions between hard and soft segments ratio, we obtained copolymers varying in mechanical properties, processability, crystallinity, and other physical properties . However, there is no literature available about their biodegradation and bioactivity. Therefore, current work examines the effect of segmental composition and the enzymatic degradation on physico-chemical properties of the copolymers by monitoring the molecular weight change and mass loss, thermal properties, and water uptake. The bioactivity of the copolymers was evaluated in simulated body fluid (SBF). In addition, the cytotoxicity of the copolymers was assessed using L292 fibroblast cells in direct contact to further determine the suitability of new copolymers for medical applications. With their already proved processability via filament fused deposition and electrospinning, the comprehensive understanding of their degradation behavior and cell-material interaction will shade more light on their potential for medical applications, where the fabrication of complex multiscale structures would bring new medical devices.