AbstractPoly(ɛ‐caprolactone)‐block‐poly(L‐lactide) (PCL‐b‐PLLA) diblock copolymer and its electrospun mats (EMs) are characterized for their microstructural, thermal, and physico‐mechanical properties. The EMs of synthesized copolymer exhibiting the optimal level of average fiber diameter (Co‐FD) and diameter variation (Co‐SD) are obtained following Taguchi's design of experiments (DOE). Electrospinning process parameters such as solution concentration, DMF content in CF/DMF solvent mixture, and applied voltage are varied at three different levels (L9). Analysis of variance (ANOVA) indicated DMF content to be the major influencing factor on FD and SD of EMs with ∼95% confidence. Regression model indicated ∼88% accuracy in predicting the FD of the copolymer‐based EMs. The physico‐mechanical properties of the optimized EMs are evaluated vis‐à‐vis the influence of FD and SD on the mechanical properties. Atomic force microscopy revealed solvent evaporation induced radial inconsistencies, desirable in terms of nanoscale surface roughness, which is higher for Co‐SD (∼600 nm) than in Co‐FD (∼400 nm). The swelling and weight loss showed marked improvement in PCL‐b‐PLLA based EMs reiterating the possibility of their enhanced compatibility as biomedical materials.