We report for the first time a polycaprolactone-human serum albumin (PCL-HSA) membrane with bimodal structures comprised of spider-web-like nano-nets and conventional fibers via facile electrospinning/netting (ESN) technique. Such unique controllable morphology was developed by electrospinning the blend solution of PCL (8 wt% in HFIP 1,1,1,3,3,3,-Hexafluoro-2-propanol) and HSA (10 wt% deionized water). The phase separation during electrospinning caused the formation of bimodal structure. Various processing factors such as applied voltage, feeding rate, and distance between nozzle tip and collector were found responsible for the formation and distribution of the nano-nets throughout the nanofibrous mesh. Field emission electron microscopy (FE-SEM) confirmed that the nano-nets were composed of interlinked nanowires with an ultrathin diameter (10-30 nm). When compared with a pure PCL membrane, the membrane containing nano-nets was shown to have better support for cellular activities as determined by cell viability and attachment assays. These results revealed that the blending of albumin, a hydrophilic biomolecule, with PCL, a hydrophobic polymer, proves to be an outstanding approach to developing membranes with controlled spider-web-like nano-nets for tissue engineering. (C) 2016 Elsevier Inc. All rights reserved.