A vital characteristic of a nanofibrous scaffold for regenerative medicine is its ability to degrade in vivo at the same rate that a damaged tissue regenerates, while maintaining its mechanical properties for structural support. This work explores the degradation kinetics and mechanical properties of extruded nanofibers fabricated through blending two commonly utilized polyesters, poly(lactic acid) and poly(ε-caprolactone). Morphological effects are correlated to degradation rates of extruded nanofibers and reveal that morphology was coupled both to the blend composition and the multilayer coextrusion processing technique. Furthermore, the correlation of the resulting mechanical properties provides improved insights into the structure–property dynamics between hydrolysis and residual mechanical properties for semicrystalline polymers to better predict scaffold performance.