Unique mechanical properties, miscibility potency, and biodegradability are the three prominent features of polycaprolactone (PCL), making it an attractive biomaterial which commonly applied in regenerative medicine and biomedical engineering. Different strategies developed for fabricating nanofibrous construct, electrospinning is a practical, simple, and efficient technique based on electro-hydrodynamic systems that use an electrified viscous fluid jet drawn by the air toward a collector at a changing electric potential. PCL electrospun-based nanofibrous composites as proper scaffolds are employed in stem cell-related research, particularly in tissue engineering, wound dressing, and systems designed for sending drugs. A compilation of mechanochemical properties and most common biological performance on PCL-based electrospun fibrous structures in biomedical application are included in this study. Therefore, electrospun PCL nanofiber applying has been presented, and after that, current progress and prospects have been discussed. Literature reviews revealed that electrospun PCL nanofibrous composites had gained significant attention in regenerative medicine, and these structures have shown notable development in mechanobiological properties. This evidence is a crucial success for biomedical strategies, especially in regenerative medicine.